Method and System for Production of Oxalic Acid and Oxalic Acid Reduction Products

ABSTRACT

The present disclosure is a method and system for production of oxalic acid and oxalic acid reduction products. The production of oxalic acid and oxalic acid reduction products may include the electrochemical conversion of CO 2  to oxalate and oxalic acid. The method and system for production of oxalic acid and oxalic acid reduction products may further include the acidification of oxalate to oxalic acid, the purification of oxalic acid and the hydrogenation of oxalic acid to produce oxalic acid reduction products.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit under 35 U.S.C. §120 of PCTapplication, International application No. PCT/US2013/077610 filed Dec.23, 2013. PCT application, International application No.PCT/US2013/077610 filed Dec. 23, 2013 is incorporated by reference inits entirety.

PCT application, International application No. PCT/US2013/077610 filedDec. 23, 2013 claims the benefit under 35 U.S.C. §119(e) of U.S.Provisional Application Ser. No. 61/745,204 filed Dec. 21, 2012, U.S.Provisional Application Ser. No. 61/794,230 filed Mar. 15, 2013, U.S.Provisional Patent Application Ser. No. 61/816,531 filed Apr. 26, 2013,U.S. Provisional Patent Application Ser. No. 61/844,755 filed Jul. 10,2013 and U.S. Provisional Patent Application No. 61/846,944 filed Jul.16, 2013. Said U.S. Provisional Application Ser. No. 61/745,204 filedDec. 21, 2013, U.S. Provisional Application Ser. No. 61/794,230 filedMar. 15, 2013, U.S. Provisional Patent Application Ser. No. 61/816,531filed Apr. 26, 2013, U.S. Provisional Patent Application Ser. No.61/844,755 filed Jul. 10, 2013 and U.S. Provisional Patent ApplicationNo. 61/846,944 filed Jul. 16, 2013 are hereby incorporated by referencein their entireties.

PCT application, International application No. PCT/US2013/077610 filedDec. 23, 2013 claims the benefit under 35 U.S.C. §120 of U.S. patentapplication Ser. No. 13/724,996 filed Dec. 21, 2012. U.S. patentapplication Ser. No. 13/724,996 claims the benefit under 35 U.S.C.§119(e) of U.S. Provisional Application Ser. No. 61/720,670 filed Oct.31, 2012, U.S. Provisional Application Ser. No. 61/703,232 filed Sep.19, 2012 and U.S. Provisional Application Ser. No. 61/675,938 filed Jul.26, 2012. Said U.S. patent application Ser. No. 13/724,996, said U.S.Provisional Application Ser. No. 61/720,670 filed Oct. 31, 2012, U.S.Provisional Application Ser. No. 61/703,232 filed Sep. 19, 2012 and U.S.Provisional Application Ser. No. 61/675,938 filed Jul. 26, 2012 areincorporated by reference in their entireties.

TECHNICAL FIELD

The present disclosure generally relates to the field of electrochemicalreactions, and more particularly to a method and system for productionof oxalic acid and oxalic acid reduction products.

BACKGROUND

The combustion of fossil fuels in activities such as electricitygeneration, transportation, and manufacturing produces billions of tonsof carbon dioxide annually. Research since the 1970s indicatesincreasing concentrations of carbon dioxide in the atmosphere may beresponsible for altering the Earth's climate, changing the pH of theocean and other potentially damaging effects. Countries around theworld, including the United States, are seeking ways to mitigateemissions of carbon dioxide.

A mechanism for mitigating emissions is to convert carbon dioxide intoeconomically valuable materials such as fuels and industrial chemicals.If the carbon dioxide is converted using energy from renewable sources,both mitigation of carbon dioxide emissions and conversion of renewableenergy into a chemical form that can be stored for later use will bepossible.

SUMMARY OF THE PREFERRED EMBODIMENTS

The present disclosure is directed to a method and system for productionof oxalic acid and oxalic acid reduction products. The production ofoxalic acid and oxalic acid reduction products may include theelectrochemical conversion of CO₂ to oxalate and oxalic acid. The methodand system for production of oxalic acid and oxalic acid reductionproducts may further include the acidification of oxalate to oxalicacid, the purification of oxalic acid and the hydrogenation of oxalicacid to produce oxalic acid reduction products.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not necessarily restrictive of the present disclosure. Theaccompanying drawings, which are incorporated in and constitute a partof the specification, illustrate subject matter of the disclosure.Together, the descriptions and the drawings serve to explain theprinciples of the disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The numerous advantages of the disclosure may be better understood bythose skilled in the art by reference to the accompanying figures inwhich:

FIG. 1 is a schematic illustrating a system for the electrochemicalreduction of carbon dioxide to oxalate; the conversion of oxalate tooxalic acid; and the conversion of oxalic acid to other products.

FIG. 2 is a schematic illustrating a system for the electrochemicalreduction of carbon dioxide to oxalate; the conversion of oxalate tooxalic acid; and the conversion of oxalic acid to other products.

FIG. 3 is a schematic illustrating a system for the electrochemicalreduction of carbon dioxide to oxalate; the conversion of oxalate tooxalic acid; and the conversion of oxalic acid to other products.

FIG. 4 is a schematic illustrating a process for converting oxalatesalts to oxalic acid.

FIG. 5 is a schematic illustrating a process for converting oxalatesalts to oxalic acid.

FIGS. 6A-6C are schematics illustrating hydrogenation devices forreducing oxalic acid to products.

FIG. 7 is a schematic illustrating an electrochemical cell forconverting oxalate salts to oxalic acid.

FIG. 8 is a schematic illustrating a system for converting carbondioxide to oxalic acid.

FIGS. 9A-9C are schematics illustrating a electrochemical cells forconverting carbon dioxide to oxalic acid.

FIG. 10 is a schematic illustrating a system for the conversion ofcarbon dioxide to mono-ethylene glycol.

FIG. 11 is a schematic illustrating a system for the conversion ofcarbon dioxide to mono-ethylene glycol.

FIG. 12 is a schematic illustrating a system for the conversion ofcarbon dioxide to mono-ethylene glycol.

FIG. 13 is a schematic illustrating a system for the conversion ofcarbon dioxide to mono-ethylene glycol.

FIG. 14 is a schematic illustrating a system for the conversion ofcarbon dioxide to mono-ethylene glycol and other two-carbon products.

FIG. 15 is a schematic illustrating the possible intermediates in thecatalytic hydrogenation of oxalic acid to mono-ethylene glycol.

FIG. 16 is a schematic illustrating the components of a thermalcatalytic hydrogenation system.

FIG. 17 is a schematic illustrating a reactive distillation column.

FIG. 18 is a schematic illustrating a process for the conversion ofcarbon dioxide to two-carbon products such as mono-ethylene glycol.

FIG. 19 is a schematic illustrating a process for purifying oxalic acid.

FIG. 20 is a schematic illustrating a process for purifying oxalic acid.

FIG. 21 is a schematic illustrating a process for purifying oxalic acid.

FIG. 22 is a schematic illustrating a process for purifying oxalic acid.

FIG. 23 is a schematic illustrating an electrochemical acidificationcell and a process for the conversion of oxalate to oxalic acid.

FIG. 24 is a schematic illustrating a process for the conversion of anoxalate salt to oxalic acid.

FIG. 25 is a schematic illustrating a process for the electrochemicalreduction of halide and trihalide.

FIG. 26 is a schematic illustrating a process for the conversion ofoxalic acid to mono-ethylene glycol.

FIG. 27 is a schematic illustrating a process for the conversion ofoxalic acid to mono-ethylene glycol.

FIG. 28 is a schematic illustrating an electrochemical process for theconversion of carbon dioxide to oxalate.

FIG. 29 is a schematic illustrating an integratedacidification-esterification-hydrogenation system.

FIG. 30 is a schematic illustrating an integratedacidification-esterification-hydrogenation system is shown.

DETAILED DESCRIPTION

Reference will now be made in detail to the subject matter disclosed,which is illustrated in the accompanying drawings.

The present disclosure is directed to a method and system for productionof oxalic acid and oxalic acid reduction products.

Before any embodiments of the disclosure are explained in detail, it isto be understood that the embodiments may not be limited in applicationper the details of the structure or the function as set forth in thefollowing descriptions or illustrated in the figures. Differentembodiments may be capable of being practiced or carried out in variousways. Also, it is to be understood that the phraseology and terminologyused herein is for the purpose of description and should not be regardedas limiting. The use of terms such as “including,” “comprising,” or“having” and variations thereof herein are generally meant to encompassthe item listed thereafter and equivalents thereof as well as additionalitems. Further, unless otherwise noted, technical terms may be usedaccording to conventional usage. It is further contemplated that likereference numbers may describe similar components and the equivalentsthereof.

The following definitions are used: TAA—tetraalkylammonium;TAAX—tetraalkylammonium halide; TBA—tetrabutylammonium;TBAX—tetrabutylammonium halide; TBABr—tetrabutylammonium bromide;TBAP—tetrabutylammonium perchlorate; TPABr—tetrapropylammonium bromide;TBAOx or TBA₂Ox or TBAO—tetrabutylammonium oxalate; PC—propylenecarbonate; ACN—acetonitrile; CO₂—carbon dioxide; HBr—Hydrobromic acid;BUTY—Gamma butyrolactone, γ-butyrolactone; OA—oxalic acid; DEO—diethyloxalate; DMO—dimethyl oxalate; EtOH—ethanol; BuOH—butanol; DBO—dibutyloxalate

Electrochemical conversion of CO₂ to oxalate may be undertaken innon-aqueous media to achieve high yields. However, oxalate is a saltthat has limited utility. The acid form of oxalate, oxalic acid, hasmany more industrial uses and may advantageously be used as anintermediate for the production of a large variety of chemical compoundssuch as glyoxylic acid, glyoxylate, glycolic acid, glycolate, glyoxal,glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, ethanol,ethane, ethylene, and certain metal oxalates such as ferrous oxalate. Aneconomical process of acidifying oxalate to oxalic acid in a combinedprocess with CO₂ to oxalate conversion is therefore advantageous. Asused herein, it should be understood that ethylene glycol may also bereferred as monoethylene glycol and mono-ethylene glycol and may besimply referred as (MEG). As used herein, ethylene glycol, mono-ethyleneglycol, monoethylene glycol and MEG may be used interchangeably and mayrefer to the chemical of C₂H₆O₂.

A second problem in non-aqueous CO₂ electrochemical conversion isfinding an appropriate anodic process. Halogens may be produced, butthese are not always marketable because of their high toxicity. Thepresent disclosure may include a method and system for production ofoxalic acid and oxalic acid reduction products which advantageouslyproduces no toxic compounds. When production of a halogen is desired,however, another embodiment may include the anodic generation of ahalogen and cathodic production of oxalate or oxalic acid depending uponthe specific process employed.

Referring to FIG. 1, a schematic illustrating a system 100 for theelectrochemical reduction of carbon dioxide to oxalate; the conversionof oxalate to oxalic acid; and the conversion of oxalic acid to otherproducts is shown. System 100 may be configured for production of oxalicacid and oxalic acid reduction products in accordance with an embodimentof the present disclosure.

It is contemplated that system 100 may operate according to the overallchemical equation:

4CO₂+2H₂O→2H₂C₂O₄+O₂  [1]

Advantageously, a halogen and halide salt may be recycled and may not beconsumed in the reactions of system 100.

System 100 may include an electrochemical cell (also referred as acontainer, electrolyzer, or cell) 102. Electrochemical cell 102 may beimplemented as a divided cell. The divided cell may be a dividedelectrochemical cell. Electrochemical cell 102 may include a firstregion 116 and a second region 118. First region 116 and second region118 may refer to a compartment, section, or generally enclosed space,and the like without departing from the scope and intent of the presentdisclosure. First region 116 may include a cathode 122. Second region118 may include an anode 124. First region 116 may include a catholyte,the catholyte including carbon dioxide which may be dissolved in thecatholyte. Second region 118 may include an anolyte which may include MX117.

Electrochemical cell 102, and all electrochemical cells describedherein, uses an energy source, not shown, which may generate anelectrical potential between the anode 124 and the cathode 122. Theelectrical potential may be a DC voltage. Energy source 114 may also beconfigured to supply a variable voltage or constant current toelectrochemical cell 102 or any electrochemical described herein.

Separator 120 may selectively control a flow of ions between the firstregion 116 and the second region 118. Separator 120 may include an ionconducting membrane, separator, or diaphragm material.

Electrochemical cell 102 is generally operational to reduce carbondioxide in the first region 116 to a first product, such as an oxalate.Oxalate 113 may be referred as an oxalate salt and may include a generalformula of M_(n)C₂O₄ where N=1 or 2. Oxalate 113 may be recoverable fromthe first region 116 while a second product, such as a halogen ortrihalide anion 115, may be recoverable from the second region 118.Carbon dioxide source 106 may provide carbon dioxide to the first region116 of electrochemical cell 102. In some embodiments, the carbon dioxideis introduced directly into the region 116 containing the cathode 122.It is contemplated that carbon dioxide source 106 may include a sourceof a mixture of gases in which carbon dioxide has been separated fromthe gas mixture.

It is contemplated that a first product, such as oxalate, may beextracted by a first product extractor, not shown. First productextractor may implement an organic product and/or inorganic productextractor. First product extractor may be generally operational toextract (separate) the first product, such as oxalate 113, from thefirst region 116. The extracted oxalate 113 may be presented through aport of the system 100 for subsequent storage and/or consumption byother devices and/or processes.

The anode side of the reaction occurring in the second region 118 ofelectrochemical cell 102, and any other electrochemical cells describedherein, may include MX 117 supplied to the second region 118. MX 117 mayalso comprise MX₂ if two anions are need for charge balance. Salt MX 117may act as both an anodic reactant as well as a supporting electrolyte.The second product recoverable from the second region 118 may be ahalogen or trihalide ion 115. MX 117 may include a cation, as M may beLi⁺, Na⁺, K⁺, Ca⁺⁺, Ba⁺⁺, Sr⁺⁺, Mg⁺⁺, a R₁R₂R₃R₄N⁺, K⁻ where each ofR₁₋₄ is independently selected from the group consisting of alkyl,branched alkyl, cycloalkyl, and aryl, tetraalkyl ammonium,tetramethylammonium, tetraethylammonium, tetrabutylammonium,tetraphenylphosphonium, tetrabutylphosphonium, tetraethylphosphonium,tetrahexylammonium, tetraoctylammonium, methyl tributylammonium,butyltrimethylammonium, 1-n-butyl-3-methylimidazolium,1-ethyl-3-methylimidazolium, 1-ethyl-1-methylpyrrolidinium,di-n-decyldimethylammonium, choline, or ammonium. To increaseelectrolyte solubility, crown ethers, such as 12-crown-4, 15-crown-5,diphenyl-18-crown-6, and 18-crown-6, may be used with the cation such asLi⁺, Na⁺, or K⁺. The electrolyte used will also determine the type ofmembrane or separator that may be selected for the electrochemical cell102. Ionic liquids may also be employed as electrolytes, as well asCTAB, hexadecyltributyl phosphonium bromide, and the Stark catalyst. Xmay include F, Cl, Br, I, BF₄, PF₆, ClO₄, or an anion; and mixturesthereof.

It is contemplated that a second product, such as halogen or trihalideanion 115, may be extracted by a second product extractor, not shown.Second product extractor may implement an organic product and/orinorganic product extractor. Second product extractor may be generallyoperational to extract (separate) the second product, such as a halogenor trihalide anion 115, from the second region 118. The extractedhalogen or trihalide anion 115 may be presented through a port of thesystem 100 for subsequent storage and/or consumption by other devicesand/or processes. It is contemplated that first product extractor 110and/or second product extractor 112 may be implemented withelectrochemical cell 102, or may be remotely located from theelectrochemical cell 102. Additionally, it is contemplated that firstproduct extractor and/or second product extractor 112 may be implementedin a variety of mechanisms and to provide desired separation methods,such as fractional distillation or molecular sieve drying, withoutdeparting from the scope and intent of the present disclosure.

In one embodiment, electrochemical cell 102 may reduce CO₂ to an oxalatesalt (M₂O₂O₄) at the cathode 122 and may oxidize a halogen containingsalt of the formula MX, where M is a cation and X is a halide anion, atthe anode 124 produce a halogen or trihalide anion 115. This liberatesthe cation (M⁺) to be transferred across a membrane or separator 120 topair with the oxalate anion in the first region 116, or also referred asthe catholyte compartment. An oxidation resistant cation exchangemembrane or separator may be employed as the separator 120.

Halogen or trihalide anion 115 may be fed to an electrochemicalreduction cell 130. It is contemplated that electrochemical reductioncell 130 may be similar to electrochemical cell 102. For example,electrochemical reduction cell 130 may include a first region and asecond region. First region and second region may refer to acompartment, section, or generally enclosed space, and the like withoutdeparting from the scope and intent of the present disclosure. Firstregion may include a cathode. Second region 118 may include an anode124. Electrochemical reduction cell 130 may reduce halogen or trihalideanion 115 to HX 132 at the cathode and oxidizes water 134 at the anode,producing oxygen (O₂) and liberating hydrogen ions (H⁺) to betransferred across the membrane of the electrochemical reduction cell130 to generate the HX 132.

Oxalate 113 may be fed to an anion exchanger 140. Anion exchanger 140may refer to an ion exchanger that exchange negatively charged ions, theanions. Anion exchanger 140 may convert oxalate 113 to oxalic acid 144using the HX 132 produced from electrochemical reduction cell 130. Anionexchanger 140 may further produce MX 117 which may be recycled to thesecond region 118 of electrochemical cell 102.

Oxalic acid 144 may be further converted to a range of more reducedtwo-carbon (or O₂) species. Oxalic acid 144 may be fed to ahydrogenation device 150, such as a thermal catalytic hydrogenationdevice or electrochemical reduction device. Oxalic acid 144 may beconverted to an oxalic acid reduction product 152. Oxalic acid reductionproduct 152 may include two-carbon species such as glyoxylic acid,glyoxal, glycolic acid, glycolaldehyde, acetaldehyde, ethylene glycol,ethanol, acetic acid, ethane, or ethylene. Oxalic acid may also beconverted to alkyl oxalates such as dimethyl oxalate by reaction with analcohol.

Referring to FIG. 2, a schematic illustrating a system 200 for theelectrochemical reduction of carbon dioxide to oxalate; the conversionof oxalate to oxalic acid; and the conversion of oxalic acid to otherproducts is shown. System 200 may include electrochemical cell 102,electrochemical cell 210 and hydrogenation device 150.

Similar to system 100, electrochemical cell 102 of system 200 may reduceCO₂ from carbon dioxide source 106 to an oxalate salt (M₂O₂O₄) at thecathode 122 and oxidizes a halogen containing salt of the formula MX,where M is a cation and X is a halide anion, at the anode 124 to producea halogen or trihalide anion 115. This liberates the cation (M⁺) to betransferred across a membrane or separator 120 to pair with the oxalateanion in the first region 116, or also referred as the catholytecompartment. An oxidation resistant cation exchange membrane may beemployed as the separator 120.

Electrochemical cell 210, also referred to an electrochemicalacidification unit, may include three regions or compartments.Electrochemical cell 210 may include a first region 116, a second region118 and a third region 212. Third region 212 may be a central ionexchange region bounded by two cation exchange membranes or separators214, 216. First region 116 may include a cathode 116 and may be fedhalogen or trihalide anion 115 from the second region of electrochemicalcell 102. Second region 118 may include an anode 124 and may be fedwater 220. Electrochemical cell 210 may be configured to acidify theoxalate salt fed to the central ion exchange region 212 to produceoxalic acid 144. MX may be recoverable from first region 116 ofelectrochemical cell 210 and recycled to the second region 118 ofelectrochemical cell 102. In the second region 118 of electrochemicalcell 210, the anode reaction may generate hydrogen ions that passthrough the adjoining cation membrane 216 into the ion exchange region212. Oxygen 222 may be produced from the oxidation of water that may berecoverable from the second region 118. It is contemplated that thesecond region 118 of electrochemical cell 210 may include an acidelectrolyte such as sulfuric acid.

Oxalic acid 144 may be further converted to a range of more reducedtwo-carbon species. Oxalic acid 144 may be fed to a hydrogenation device150, such as a thermal catalytic hydrogenation device or electrochemicalreduction device. Oxalic acid 144 may be converted to an oxalic acidreduction product 152. It is contemplated that system 200 may operateaccording to the overall chemical equation:

4CO₂+2H₂O→2H₂O₂O₄+O₂  [2]

Referring to FIG. 3, a schematic illustrating a system 300 for theelectrochemical reduction of carbon dioxide to oxalate; the conversionof oxalate to oxalic acid; and the conversion of oxalic acid to otherproducts is shown. System 300 may include an electrochemical cell 102,an anion exchanger 140, and a hydrogenation device 150.

Similar to system 100, electrochemical cell 102 of system 300 may reduceCO₂ from carbon dioxide source 106 to an oxalate salt (M₂O₂O₄) at thecathode 122 and oxidize a halogen containing salt of the formula MX,where M is a cation and X is a halide anion, at the anode 124 to producea halogen or trihalide anion 115. This liberates the cation (M⁺) to betransferred across a membrane or separator 120 to pair with the oxalateanion in the first region 116, or also referred as the catholytecompartment. An oxidation resistant cation exchange membrane may beemployed as the separator 120.

It is contemplated that halogen or trihalide anion 115 recoverable fromthe second region 118 of electrochemical cell 102 may be extracted as asaleable product or as a product that may be used in a separate process,such as a bromination reaction with an organic producing a brominatedorganic, such as the reaction of bromine with ethane to producebromoethane, as well as other bromination reactions in producing finechemicals.

Oxalate 113 may be fed to anion exchanger 140. Anion exchanger 140 mayrefer to an ion exchanger that exchanges negatively charged ions, theanions. Anion exchanger 140 may convert oxalate 113 to oxalic acid 144using the HX received from an HX source 310. Anion exchanger 140 mayfurther produce MX 117 which may be recycled to the second region 118 ofelectrochemical cell 102. The overall chemical reaction of system 300may be represented by:

2CO₂+2HX→H₂O₂O₄+X₂  [3]

The HX source 310, configured to flow as a HX stream could be apurchased reagent in the process or could be utilized as part of alarger process scheme involving further reactions, such that the HX isrecycled—for example, from the bromination of organics, which producesan HX byproduct.

Referring to FIG. 4, a schematic illustrating a process for convertingoxalate salts to oxalic acid is shown. The inputs of the anion exchangeresin may include primary inputs such as a solvent, oxalate, and MX withregenerants such as water and HX. The anion exchange resin may produce arecycle stream that may include a solvent and MX and may produce aproduct stream of oxalic acid, water and HX. FIG. 5 is a schematicillustrating a process for converting oxalate salts to oxalic acid.Process may include an oxalate absorption process, a water rinseprocess, an oxalate desorption process 530 and a solvent rinse process.

Referring to FIGS. 6A-6C, schematics illustrating hydrogenation devices150 for reducing oxalic acid to products are shown. FIG. 6A depicts athermal catalytic hydrogenation device 610 that may receive oxalic acidand hydrogen and may produce an oxalic acid reduction product and water.FIG. 6B depicts an electrochemical hydrogenation cell 620.Electrochemical hydrogenation cell 620 may include an oxalic acid inputto the catholyte region and a water input to the anolyte region. Anoxalic acid reduction product may be recovered from the catholyte regionand oxygen may be recovered from the anolyte region of theelectrochemical reduction cell 620. FIG. 6C depicts an electrochemicalreduction cell 630 in accordance with another embodiment of the presentdisclosure. Electrochemical reduction cell 630 may include an oxalicacid input to the catholyte region and a HX input to the anolyte region.An oxalic acid reduction product may be recovered from the catholyteregion and a halogen may be recovered from the anolyte region of theelectrochemical hydrogenation cell 630. It is contemplated that thestructure of electrochemical hydrogenation cell 620, 630 may be similarto electrochemical cell 102 as previously described, including a firstregion having a cathode, such as a catholyte region and a second regionhaving an anode, such as an anolyte region. The regions may be separatedby a membrane or separator.

Referring to FIG. 7, a schematic illustrating an electrochemical cell700 for converting oxalate salts to oxalic acid is shown.Electrochemical cell 700 may reduce CO₂ to an oxalate salt (M₂O₂O₄) atthe cathode. Electrochemical cell 700 may be pre-charged with oxalicacid and the oxalate salt to enhance conductivity. The catholyte mayinclude a non-aqueous aprotic solvent such as acetonitrile or propylenecarbonate (PC). The oxalate ion may be transferred to the anolyte regionthrough an anion exchange membrane (AEM). The anode reaction may includeoxidation of water, a hydrogen halide, or any organic or inorganicspecies that when oxidized may liberate protons. The anolyte may includean aqueous solvent. The oxalate that would be transferred through theAEM would then be acidified by the generated protons to produce oxalicacid.

Referring to FIG. 8, a schematic illustrating a system 800 forconverting carbon dioxide to oxalic acid is shown. System 800 mayinclude a first electrochemical cell 810 and a second electrochemicalcell 820. In the first electrochemical cell 810, the anodic reaction inthe first electrochemical cell 810 may involve a Cu(I)/Cu(II) couple.The advantage of using this reaction may be a lower half-cell voltagerequired compared to the likely voltages for operation of theelectrochemical cell 700 of FIG. 7. Because of the low half-cell voltageachieved by using the Cu(I)/Cu(II) couple, the undesired oxidation ofoxalic acid may be minimized. Therefore, a copper oxalate salt, CuC₂O₄may be recoverable from the electrochemical cell 810. The copper oxalatesalt may be acidified in a second electrochemical cell 820. Inelectrochemical cell 820, the anodic reaction may be water splitting, oroxidation of a hydrogen halide or other organic or inorganic speciesthat under oxidation liberates protons. These protons would migrateacross a cation exchange membrane or separator to the catholyte. Thecopper oxalate salt may be acidified to oxalic acid and the Cu(II)species reduced to Cu(I) to be recycled to the anodic compartment of thefirst electrochemical cell 810. System 800 would be operable to produceoxalic acid by employing the Cu(I)/Cu(II) couple acting as a mediator tothe reaction.

Referring to FIGS. 9A-9C, schematics illustrating electrochemical cells910, 920, 930 for converting carbon dioxide to oxalic acid are shown. Ineach of electrochemical cells 910, 920, 930, a non-aqueous aproticsolvent (or solvents) is used for both the catholyte and the anolyte. Inthese modes of operation, a solvent used in the electrochemical cell910, 920, 930 may be a non-aqueous solution and the anodes ofelectrochemical cells 910, 920, 930 are fed a hydrogen gas stream. TheAEM would not be necessary, and likely a simple separator material maybe employed. In this mode of operation, the hydrogen may serve as theanodic reactant and would be oxidized to hydrogen ions. In a similarmode of operation, the oxalate salt produced in the cathode compartmentmay be acidified in the anolyte to produce oxalic acid inelectrochemical cell 910 as shown in FIG. 9A.

Referring to FIG. 9B, an electrochemical cell 920 which includes a mixof H₂/CO₂ fed into the catholyte region of the electrochemical cell 920.Electrochemical cell 920 may reduce the CO₂ to oxalate and the H₂ may beoxidized at the anode. Electrochemical cell 920 may be configured forconvective flow-through of the catholyte to the anolyte region to ensureH₂ is available anodically and CO₂ is available cathodically. This maysimplify the required gas feed to the electrochemical cell 920. Inanother embodiment, a stream of H₂ may be fed to the anolyte and a feedof CO₂ could be fed to the catholyte separately.

Referring to FIG. 9C, electrochemical cell 930 is shown. Electrochemicalcell 930 may include a liquid permeable gas separator. H₂ gas could befed either flow-by (as shown) or in a flow-through mode. It iscontemplated that electrochemical cells 910, 920, 930 may include asimilar structure as electrochemical cell 102 as previously described,unless otherwise described without departing from the scope and intentof the present disclosure.

Referring to FIG. 10, a schematic illustrating a system 1000 for theconversion of carbon dioxide to mono-ethylene glycol is shown. System1000 may include electrochemical cell 102, reactor 1010, acidificationreactor 1030 and a hydogenation device 150. In electrochemical cell 102,carbon dioxide may be reduced to an oxalate salt, at the cathode of anelectrochemical cell 102. A halide salt may be oxidized to a halogen ortrihalide anion at the anode of the electrochemical cell 102. Thereactions of electrochemical cell 102 may preferably occur in anon-aqueous solvent.

In a reactor 1010, halogen or trihalide anion produced byelectrochemical cell 102 may be reacted with hydrogen to form a hydrogenhalide. Reactor 1010 may be a burner or combustor wherein a significantamount of thermal energy is produced in addition to hydrogen halide. Thethermal energy may then be used in other operations, such asdistillation, the separation of products, and electric power generation.Alternatively, reactor 1010 may be a fuel cell. The resultingelectricity may be used in a variety of ways, for example to offset someof the electrical requirements of the CO₂ reduction in electrochemicalcell 102. Hydrogen halide from reactor 1010 may be reacted with oxalatesalt from electrochemical cell 102 in an acidification reactor 1030 toproduce a oxalic acid, and a halide salt. The halide salt may then berecycled to the electrochemical cell 102. The oxalic acid may be fed tohydrogenation device 150 where it is reduced to an oxalic acid reductionproduct, such as monoethylene glycol.

Referring to FIG. 11, a schematic illustrating a system 1100 for theconversion of carbon dioxide to mono-ethylene glycol is shown. System1100 may include electrochemical cell 102, reactor 1010, acidificationreactor 1030, esterification device 1110 and hydogenation device 150.System 1100 may include an esterfication device 1110 which may receiveoxalic acid from reactor 1030 whereby the oxalic acid is reacted with analcohol in the esterfication device 1110 to produce an oxalate ester oroxalate diester that is fed to hydrogenation device 150. In oneembodiment, the oxalate ester or oxalate diester may be hydrogenated tomake mono-ethylene glycol (MEG). Other products may include glyoxylicacid, glycolic acid, glyoxal, glycolaldehyde, acetic acid, acetaldehyde,ethanol, ethane, diethylene glycol, triethylene glycol, ethers, esters,polyglycols, unsaturated chemicals such as crotonaldehyde, alcohols,diols, carboxylic acids, aldehydes, and four carbon products. It iscontemplated that hydrogenation device may recycle the alcohol and anyoxalate ester or oxalate diester to the esterification device 1110.

Referring to FIG. 12, a schematic illustrating a system 1200 for theconversion of carbon dioxide to mono-ethylene glycol is shown. System1200 may include electrochemical cell 102, an anolyte recoveryelectrochemical cell 130, acidification reactor 1030 and hydrogenationdevice 150. Anolyte recovery electrochemical cell 130 may receive ahalogen from electrochemical cell 102. Anolyte recovery electrochemicalcell 130 may also receive water and produce HX and an oxygen byproduct.Acidification reactor 1030 is configured to receive oxalate and HX andproduce a carboxylic acid, such as oxalic acid, and a halide salt. Thehalide salt may then be recycled to the electrochemical cell 102. Theoxalic acid may be fed to hydrogenation device 150 where it is reducedto an oxalic acid reduction product, such as monoethylene glycol.

Referring to FIG. 13, a schematic illustrating a system 1300 for theconversion of carbon dioxide to mono-ethylene glycol is shown. System1300 may include an electrochemical cell 1310 which includes a hydrogenfed anode, an esterification device 1110 and a hydrogenation device 150.Electrochemical cell 1310 may be implemented as electrochemical cells910, 920, 930 as shown in FIGS. 9A-9C.

Referring to FIG. 14, a schematic illustrating a system 1400 for theconversion of carbon dioxide to mono-ethylene glycol and othertwo-carbon products. System 1400 may include electrochemical cell 102,acidification reactor 1030 and hydogenation device 150. Hydrogen halidemay be reacted with carboxylate salt, such as an oxalate, fromelectrochemical cell 102 in an acidification reactor 1030 to produce acarboxylic acid, such as oxalic acid, and a halide salt. The halide saltmay then be recycled to the electrochemical cell 102. The oxalic acidmay be fed to hydrogenation device 150 where it is reduced to an oxalicacid reduction product, such as monoethylene glycol.

In addition to mono-ethylene glycol, systems 1000, 1100, 1200, 1300 and1400 may produce a variety of multi-carbon chemicals. If oxalic acid isproduced, it may be further reduced, for example, by electrochemicalreduction, catalytic reduction or other reduction methods.

Electrochemical Cell Operating Conditions

Referring once again to electrochemical cell 102 as shown in at leastFIG. 1, a solvent may be employed. The solvent may be a non-aqueoussolvent or mix of solvents including propylene carbonate, ethylenecarbonate, dimethyl carbonate, diethyl carbonate, dimethylsulfoxide,dimethylformamide, acetonitrile, ammonia, acetone, tetrahydrofuran,N,N-dimethylacetaminde, dimethoxyethane, diethylene glycol dimethylester, butyrolnitrile, 1,2-difluorobenzene, γ-butyrolactone,N-methyl-2-pyrrolidone, sulfolane, 1,4-dioxane, nitrobenzene,nitromethane, acetic anhydride, alkanes, cycloalkanes, perfluorocarbons,linear carbonates, aromatics such as benzene and toluene and theirderivatives, dichloromethane, chloroform, ethers, chlorobenzene,polyols, glymes, diglymes, triglymes, tetraglymes, alcohols, alkenes,trifluorotoluene, anisole, m-cresol, and ionic liquids to include thosecontaining cations of the types: 1,3 dialkyimidazolium, N,Ndialkylpyrrolidinium, and 1-alkyl-2,3-dimethylimidazolium where N=2 or 4and anions of the type hexafluorophosphate, tetrafluroborate,bis(trifluoromethanesulfonyl)imide, perfluoroalkylphosphate, and halideions such as Br—.

Many cathode materials may be used to effect the reduction of CO₂ tooxalate. Cathode materials may include Al, Au, Ag, Bi, Carbon (e.g.graphite), Cd, Co, Cr, Cu, Cu₂O, Cu alloys (e.g., brass and bronze), Fe,Fe alloys (e.g. Fe—Ti), Ga, Hg, In, Mo, Mo alloys (e.g. Mo—Ni), Nb, Ni,NiCo₂O₄, Ni alloys (e.g., Ni 625, NiHX), Ni—Fe alloys, Pb, Pb alloys, Pdalloys (e.g., PdAg), Pt, Pt alloys (e.g., PtRh), Rh, Sn, Sn alloys(e.g., SnAg, SnPb, SnSb), Ti, V, W, W alloys, Zn, stainless steel (SS)(e.g., SS 2205, SS 304, SS 316, SS 321), austenitic steel, ferriticsteel, duplex steel, martensitic steel, Nichrome in various ratios(e.g., NiCr 60:16 (with Fe)), elgiloy (e.g., Co—Ni—Cr), and variousHaynes International Inc. trade name nickel-cobalt alloys calledHastelloys, such as Hastelloy 276, Hastelloy C. Metal carbides ascathodes may also be used and could include iron carbide, molybdenumcarbide, and chromium carbide.

A range of screens/meshes, non-woven materials, sintered metals, layeredmaterials, foams, and gradients are suitable for use as cathodematerials for the electrochemical cell. Cathodes may be coated withnanoparticles and nano-features through template electroplating,etching, and deposition. For example, nickel nanoparticles may be usedto coat the cathode surfaces. An exemplary cathode may comprise ofmultilayers of 316 SS screen made of alternating layers of 400 mesh and15 mesh stainless steel. A quantity of 12 or 22 micron non-woven 316stainless steel, such as those available from Bekaert, may be used as aflow channel/electrical contact between the back plate and the layeredmesh assembly. Another cathode may comprise corrugated screens with flowchannels built in, wherein layers are spot welded or sintered together.The 3D electrode may be sintered or welded to suitable thickness 316 SSplate current distributor to make a complete integrated cathodeassembly.

Cathode structures

Suitable cathode structures also include the following forms:

Metal plates

Packed bed consisting of metal spheres or fibers

Assembly of screens/meshes

Metal foams

Metal non-woven materials including needeled felts

Sintered or partially sintered non-wovens

Metal wools

Layered materials

Layered metal meshes or screens

Welded layered meshes, such as those used as filtration media for PEextrusion

Sintered metal fibers and powders

Woven metal felts

Other metal woven fibrous metals in various weaves or twills comprisingvarious metal fiber sizes and thicknesses

Metal coated carbon materials, such as nickel on carbon fibers, or metalcoated ceramic fibers

The electrochemical cell cathode may also comprise one or more cathodematerials, one or more structure types, and with one or morecombinations of metal and metal coating compositions. For example, thecathode may consist of a nickel fiber structure adjacent to theseparator, and utilize a 304 SS structure towards the cathode backplate,which may be 304 SS or another metal alloy. The selection of the metalalloys and metallic coatings on the cathode is used to maximize thecathode reduction of carbon dioxide reaction. Cathode coatings on thecathode structure materials may be applied by electroplating, chemicalvapor deposition (CVD) or other methods to all or various sections ofthe cathode structure. The cathode coatings may be metal or metaloxides, or converted to the metal or oxide by hydrogen reduction (metaloxide to metal) or thermal oxidation in air (formation of oxidecoatings). The metals are the same group noted as the single metals oralloys specified. The coatings may also consist of multiple coatings ofdifferent layers of materials for providing stability.

Table 0 shows the effect of cathode materials on oxalate faradaic yieldoperated at constant current of −3.5 to ˜5 mA/cm². The workingelectrode, as listed, was immersed in a 0.2M TBABr solution in propylenecarbonate saturated with CO₂. The reference electrode was a Ag wire. Athree chamber electrochemical cell was used, with the compartmentsseparated by porous glass frits. A two compartment electrochemical cellwas used in some cases, the compartments separated by a Vicor® glassfrit. The counter electrode was a Zn foil immersed in 0.2Mtetrabutylammonium perchlorate (TBAP) in propylene carbonate.

Typically, the water content was 100-200 ppm at the start of theexperiment and 120-150 at the end of the experiment. Experiments weretypically run for 6 hrs. Approximately 10% Faradaic yield of oxalate waslost to the center compartment chamber when the three compartment cellwas used, therefore true oxalate Faradaic yields are typically higherthan listed.

TABLE 0 Oxalate FY Cathodes (%) Stainless steel 2205 47-56 Stainlesssteel 304 63-85 Stainless steel 316 50-72 Ni:Cr (60:16) 40-53 Ni:Cr(80:20)  80-100 Ni:Fe:Mo 68-86 Ni (99.994% purity) 74-80 Nickel 58-67 Mo72 Fe:Co (80:20)  68* Co:Cr:Mo (60:30:10)  0 Hastelloy C Mesh 28-35 Co73-85 W 78-88 Cu:Ni (55:45) 31 Fe:Mo (80:20)  72* Co:Cr:Mo (60:30:10) 68* Fe:Ni:B:Mo Metallic Glass  6* FeTi  0* FeB  0* MoB₂  2* Ni:Mo(80:20)  37* Mo:Ti (80:20)  9* W:Co (50:50)  2* WC:Co (94:6)  0*Represents the average of 2-3 independent experiments

In addition, the cathode material could be chemically modified toimprove or enhance the cathode reaction efficiency and selectivity. Formetallic surfaces, modification may include using thiols, primaryamines, pyrrolidones, heterocyclic amines, and surfactants containingcarboxylate groups, phosphonate groups, phosphine groups, and citrategroups. For oxide and carbide materials, silanes, diazomethanes, alkylammonium ions, cycloketones, cycloalkylidenes, and ionic liquid cationsmay be employed to modify the cathode surfaces.

To passivate stainless steel electrodes, electrodes of a required sizeare cut from bulk material. The electrodes are cleaned by polishing withalumina powder, followed by rinsing with deionized water, then dippingin acetone for approximately 2 minutes, followed by rinsing andsonication in deionized water. A 15 wt % citric acid in deionized watersolution is prepared. Cleaned electrodes are immersed in 15 wt %solution of citric acid for approximately four hours at room temperature(25° C.). The electrodes are taken out of the solution, rinsed 3 timeswith deionized water and dried under argon. Treated electrodes may thenbe stored in closed glass vials until needed.

It is contemplated that the high surface area cathode/anode electrodemay include the following characteristics, such as a preferred voidvolume ranging from 30% to 98%. The electrodes may include specificsurface areas from 2 cm²/cm³ to 500 cm²/cm³ or higher. Surface areasalso may be defined as total area in comparison to the currentdistributor/conductor back plate, with a preferred range of 2× to 1000×or more.

Table 00 shows the effect of corrosion inhibitors on oxalate faradaicyield when an electrochemical cell is operated at constant current of−3.5 mA/cm². The working electrode (304 SS) was immersed in a 0.2M TBABrsolution in propylene carbonate saturated with CO₂. The referenceelectrode was a Ag wire. A three chamber electrochemical cell was used,with the compartments separated by porous glass frits. The counterelectrode was a Zn foil immersed in 0.2M TBAP in propylene carbonate.

TABLE 00 Cathode Concentration (ppm) Yield Oxalate (%) Imidizole 50045.5 +/− 26% 2-pyrrolydinone 500 82.4 +/− 6.4% EDTA 500 82.2

Electrochemical Flow Cell Examples

An electrochemical cell was assembled with a 316 SS back conductor plateon the cathode side and a graphite back conductor plate on the anodeside. A single layer of hydrophobic PVDF with a pore diameter of about0.45 micron and thickness of about 150 micron was used as a separatorbetween the cathode compartment and anode compartment. The cathodecompartment contained a multi-layered high surface area 316 SS cathode.The cathode consisted of a non-woven fiber mat with a fiber diameter of22 micron, which was in direct contact with the back plate. Thethickness of the fiber mat was approximately 0.5 mm in its compressedstate when installed in the cell. Between the non-woven material and theseparator an assembly of layers of mesh was placed having twoalternating opening sizes, fine (400×400) mesh with a thickness of 0.15mm and an opening size of 0.0015 inches and an open area of 38%, and acoarse (15×15) mesh with a thickness of 0.4 mm and an opening size of0.057 inches and an open area of 73%. In total eight layers of mesh wereused. A 0.35 mm thick porous PTFE screen was placed between theseparator and the cathode to minimize the risk of a short circuit. Theanode compartment contained 4 layers of carbon cloth, the first of whichwas in direct contact with the separator. A sheet of porous glassycarbon, i.e., reticulated vitreous carbon with a pore density of 60pores per inch, was placed between the layer and the other 3 carboncloth layers. The thickness of a single carbon cloth layer and the RVCwas 0.35 mm and 3.65 mm, respectively. Both electrode compartments wereassembled in a zero-gap configuration, i.e., no open space left oneither side of the separator.

The electrochemically active area of the cell was in the range of 50-100cm². Electrolyte was fed to the respective electrodes via high densitypolyethylene flow plates having flow channels with a circular crosssection. The flow entered the active electrode compartment on the bottomof the cell and was directed upward, parallel to the separator.

Example 1 PC Room Temperature Operation

A flow cell experiment was run using propylene carbonate with 0.5 MTBABr as the electrolyte. The anolyte and catholyte were purged withnitrogen and sparged with carbon dioxide, respectively. The currentdensity was 75 mA/cm2 and was conducted at room temperature (25° C.).The flow rate for the catholyte was 150 ml/min and for the anolyte was100 ml/min. The cell voltage was about 15V. The current efficiency wasapproximately 30% while the highest oxalate concentration was 0.37% byweight (3700 ppm).

Example 2 PC High Temperature Operation

A flow cell experiment was executed using propylene carbonate with 0.5 MTBA-Br and 10 mM benzonitrile as the electrolyte. The anolyte andcatholyte were purged with nitrogen and sparged with carbon dioxide,respectively. The current density was 75 mA/cm² and was conducted at 60°C. The flow rates for both the anode and cathode were 1.1 L/min. Thecell voltage was between 6.8 and 7 volts. The current efficiency wasbetween 15% and 30%. The highest oxalate concentration was 0.24% byweight (2400 ppm).

Example 3 ACN as a Anolyte/Catholyte Solvent

A flow cell experiment was performed using acetonitrile as a solventwith 0.75 M TBABr as the electrolyte. The anolyte and catholyte werepurged with nitrogen and sparged with carbon dioxide, respectively. Thecurrent density was 75 mA/cm2. The run was conducted at ambienttemperature and pressure. The anode and cathode flow rate was 1.1 L/min.The cell voltage was in the range of 5.7-6.5 V. The current efficiencywas 50% for oxalate and 40% for the anolyte tribromide generation. Thehighest oxalate concentration was 2.5% by weight (25,000 ppm).

Example 4 Nickel Cathode

In an embodiment of the disclosure, it has been found that nickelcathodes may improve cell voltages. When using stainless steel cathodes,voltages of 5.5V at 75 mA/cm2 are typically observed. With thick Nicathodes voltages of about 5 V or less are observed. (Table 1). As shownin Table 2, a thin electrode configuration in conjunction with Ni bringsthe voltage to about 4.1V. Both tests were executed with a PTFEseparator (0.45 micron pore size). A PVDF separator (0.1 micron poresize) may also be used. A test of a PTFE separator using a stainlesssteel cathode resulted in yields similar to what is shown on Table 1(about 70% for the first hour of the run, see Table 3).

The nickel cathode may be formed as a mesh including either 2 or 4layers of mesh bonded together. To form the cathodes used in theexperiments, three to five pieces of mesh were cut (depending on cathodethickness), which were then folded once, yielding 6 or 10 layers ofbonded mesh in the cathode compartment. The current collector plate mayalso comprise nickel.

TABLE 1 Thick Nickel Cathode Run With PTFE Separator Cell Configuration:5x double layer (folded) of multi-layer Ni-mesh [85 × 70 0.006], 1 PTFEScreen, 0.45 micron PTFE hydrophilic separator (rough side facing anode.Description: Run with 0.75M TBA-Br in ACN thick electrode configuration(¼″) Oxalate Faradaic I Cell Oxalate Yield % Time Current VoltageConcentration At Time (min) (Amperes) (Volts) mg/L Intervals 0 7.7 5.06593.60 30 7.7 4.74 2953.98 77.9% 60 7.7 4.82 5293.01 75.2%

TABLE 2 Thin Nickel Cathode Run With PTFE Separator Cell Configuration:3x double layer (folded) of multi-layer Ni-mesh [85 × 70 0.006], 0.45micron PTFE hydrophilic separator (rough side facing anode) Description:Run with 0.75M TBA-Br, thin electrode configuration (⅛″) OxalateFaradaic I Cell Oxalate Yield % Time Current Voltage Concentration AtTime (min) (Amperes) (Volts) mg/L Intervals 0 7.7 4.36 413.52 30 7.74.14 2356.78 64.4% 60 7.7 4.05 4017.87 54.4% 90 7.7 4.09 5543.32 49.5%120 7.7 4.06 6839.26 42.2%

TABLE 3 Stainless Steel Cathode with PTFE separator Cell configuration:PTFE, hydrophilic PTFE separator. (0.45 μm), C cloth Run Description:Run with 0.75M TBABr in ACN, 0.45M hydrophilic PTFE separator OxalateFaradaic I Cell Oxalate Yield % Time Current Voltage Concentration AtTime (min) (Amperes) (Volts) mg/L Intervals 0 7.7 6.11 122.27 30 7.77.04 2139.99 69.0% 60 7.7 6.74 4116.19 67.1% 90 7.7 6.82 5979.04 55.0%120 7.7 6.95 7738.92 56.8%

It is further contemplated that additives may be utilized to increasesalt solvation and conductivity in electrochemical cell 102. Additivesmay be used to enhance salt solvation and may also increase conductivityin an additive or co-solvent role. Additive concentrations may rangefrom ppm levels to 100% by weight. In general, the additive or multipleadditives will be used in addition to one or more solvents listed above.Additives may include carbonates such as dimethyl carbonate, ethylmethylcarbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.Carbonates with other akyl groups are also claimed. In additionphosphates such as benzyl phosphate, denzyl dimethyl phosphate, allylphosphate, dibenzyl phosphate, and diallyl phosphates may be used. Someorganic sulfates such as methyl benzyl sulfate, ethylbenzylsulfate,diallyl sulfate, propyl allyl sulfate and butylallylsulfate may also beused as additives to increase the conductivity.

Additives may also include the ionic liquids listed previously as wellas their mixtures and other variations. Surfactants may also be used.Crown ethers may be added to increase the solvation of hard cations suchas Li⁺, Na⁺, and K. The crown ether employed for Li⁺, Na⁺ and K⁺ are12-crown-4, 15-crown-5, diphenyl-18-crown-6, and 18-crown-6,respectively. Similarly, cryptands may also be used to increasesolvation for hard cations. These include 2.2.2-cryptand,2.2.1-cryptand, 2.1.1-cryptand, 2.2.2B-cryptand, and5-decyl-4,7,13,16,21-pentaoxa-1,10-diazabicyclo(8.8.5)tricosane. Largercryptands and those available from EMD Millipore under the trade name ofKryptofix may also be employed.

Anion acceptors may also be used to increase solvation of the halideanion. These include borane and boroxine derivatives to include, but notlimited to, tris(isopropyl)borane and trimethoxyboroxin.

Glymes may increase conductivity, increasing ion solvation and also maylower solution viscosity. Glymes include glyme, diglyme, triglyme, andtetraglyme as well other glyme variations. Metal nanoparticles,zwitterions, and micelles or reverse micelles could also be employed.

A range of organic homogenous catalysts, capable of being reduced to aradical anion at the cathode interface and transferring an electron toCO₂ may be used. These include, but are not limited to, benzophenonemethyl 4-methyl-3-nitrobenzoate, tetracyanoquinodimethane,cyclooctatetraene, diphenylethanedione (benzil) and benzonitrile.

Anion catalysts to help effect the oxidation of halide ions to halogenscould include nitroxides, nitronyl nitroxides, azephenylenyls,perchlorophenylmethyl radicals, TEMPO(2,2,6,6-Tetramethyl-1-piperidinyloxy) and tris(2,4,6-trichlorophenyl)methyl radicals. The radical of each compound may also be used. Othercatalysts could include succinimide, N-bromosuccinimide, or otherimides.

minimum voltage for the cathodic half cell may be −0.71 V vs. SCE. Theoperating cathodic half cell voltage is usually between −1.2 and −3 Vvs. SCE. The minimum voltage for the anodic half cell is 0.83 V vs. SCE.The operating anodic half cell voltage is usually between 1 and 3 V vs.SCE. The overall voltage for the complete cell is usually between 2 and20 V.

Catholyte operating temperature may be in a range of −10 to 240° C., andmore preferably 5-60° C. The lower temperature may be limited by theelectrolytes used and their freezing points. In general, the lower thetemperature, the higher the solubility of CO₂ in the solution phase ofthe electrolyte. Higher carbon dioxide concentrations may help inobtaining higher conversion and current efficiencies. The drawback isthat the operating electrolyzer cell voltages may be higher, so there isan optimization that would be done to produce the chemicals at thelowest operating cost. Anolyte operating temperature operatingtemperature may be in a range of −10 to 240° C., more preferably 5-60°C.

Operating the electrochemical cell catholyte at a higher operatingpressure allows more dissolved CO₂ to dissolve in the solvent.Typically, electrochemical cells may operate at pressures up to about 20to 30 psig in multi-cell stack designs, although with modifications,they could operate at up to 100 psig. The electrochemical cell anolytewould also need to be operated in the same pressure range to minimizethe pressure differential on the membrane separating the two electrodecompartments. Special electrochemical designs are required to operateelectrochemical units at higher operating pressures up to about 60 to100 atmospheres or greater, which is in the liquid CO₂ and supercriticalCO₂ operating range.

In another embodiment, a portion of the catholyte recycle stream may beseparately pressurized using a flow restriction with backpressure orusing a pump, with CO₂ injection, such that the pressurized stream isthen injected into the catholyte region of the electrochemical cell, andpotentially increasing the amount of dissolved CO₂ in the aqueoussolution to improve the conversion yield.

The catholyte cross sectional area flow rate range may be 2-3,000gpm/ft² or more (0.0076-11.36 m³/m²) and may include a flow velocityrange of 0.002 to 20 ft/sec (0.0006 to 6.1 m/sec).

The electrochemical cell design may include Zero-Gap, flow-through witha recirculating catholyte electrolyte with various high surface areacathode materials. Additional designs may include flooded co-currentpacked and trickle bed designs with the various high surface areacathode materials. Bipolar stack cell designs and High pressure celldesigns may also be employed for the electrochemical cells.

The operating cell voltages for the electrochemical cells disclosed inthe embodiments in this disclosure may range from about 1.0 to about 20volts depending on the anode and cathode chemistry employed in additionto the cell operating current density. The operating current density ofthe electrochemical cells may range from 5 ma/cm² to as high as 500ma/cm² or more.

For bromine and iodine anode oxidation chemistry, carbon and graphiteare particularly suitable for use as anodes. The anode may includeelectrocatalytic coatings applied to the surfaces of the base anodestructure. For the oxidation of HBr, acid anolytes, and oxidizing watergenerating oxygen, the preferred electrocatalytic coatings may includeprecious metal oxides such as ruthenium and iridium oxides, as well asplatinum and gold and their combinations as metals and oxides on valvemetal substrates such as titanium, tantalum, zirconium, or niobium. Forbromine and iodine anode chemistry, carbon and graphite are particularlysuitable for use as anodes. Polymeric bonded carbon material may also beused. High surface area anode structures that may be used which wouldhelp promote the reactions at the anode surfaces. The high surface areaanode base material may be in a reticulated form composed of fibers,sintered powder, sintered screens, and the like, and may be sintered,welded, or mechanically connected to a current distributor back platethat is commonly used in bipolar electrochemical cell assemblies. Inaddition, the high surface area reticulated anode structure may alsocontain areas where additional applied catalysts on and near theelectrocatalytic active surfaces of the anode surface structure toenhance and promote reactions that may occur in the bulk solution awayfrom the anode surface such as the reaction between bromine and thecarbon based reactant being introduced into the anolyte. The anodestructure may be gradated, so that the density of the may vary in thevertical or horizontal direction to allow the easier escape of gasesfrom the anode structure. In this gradation, there may be a distributionof particles of materials mixed in the anode structure that may containcatalysts, such as precious metals such as platinum and precious metaloxides such as ruthenium oxide in addition to other transition metaloxide catalysts.

The electrochemical cell anode may comprise flat carbon/graphite plates,RVC (reticulated vitreous carbon) foams, carbon cloth, carbonfelts/tissue may be used. Carbon cloth may be used as an electricallyconductive material to ensure good electrical contact with the anodeback plate.

Suitable Anode structures include:

Plates (carbon/graphite/graphene)

RVC

Carbon cloth

Woven with and without activated carbon layer

Various loadings of PTFE

Carbon tissue

Carbon felts

Carbon fibers

Conductive diamond films

Iridium oxide on titanium

Ruthenium oxide plated or deposited onto a carbon felt or carbon clothas a catalyst

Graphene

Cation ion exchange type membranes may be preferred as separators for120 in embodiments for electrochemical cell 102, especially those thathave a high rejection efficiency to anions and allowing cations to pass.Examples of these membrane types having a fluorinated hydrocarbonbackbone are perfluorinated sulfonic acid based cation ion exchangemembranes such as DuPont Nafion® brand unreinforced types N117 and N120series, more preferred PTFE fiber reinforced N324 and N424 types, andsimilar related membranes manufactured by Japanese companies under thesupplier trade names such as Flemion®.

Other multi-layer perfluorinated ion exchange membranes used in thechlor alkali industry have a bilayer construction of a sulfonic acidbased membrane layer bonded to a carboxylic acid based membrane layer,which efficiently operates with an anolyte and catholyte above a pH ofabout 2 or higher. These membranes have a much higher anion rejectionefficiency. These are sold by DuPont under their Nafion® trademark asthe N900 series, such as the N90209, N966, N982, and the 2000 series,such as the N2010, N2020, and N2030 and all of their types and subtypes.

Hydrocarbon based membranes, which are made from of various cation ionexchange materials may also be used if the anion rejection is not ascritical, such as those sold by Sybron under their trade name Ionac®,AGC Engineering (Asahi Glass) under their Selemion® trade name, andTokuyama Soda among others on the market. These hydrocarbon basedmembranes may be specially prepared from ion exchange materials that arebonded together in a suitable bonding matrix such as polyethylene,polypropylene, and polyvinylchlorine (PVC) as examples. Other membranetypes may use a microporous separator and have an impregnated ionexchange material that may be chemically bonded or adhered to theseparator, such as Nafion infused or bonded to a PVDF or PTFE separator,or other ionic materials, such as ionic liquids that can be used toprepare solid gel-type membranes and the like, as long as they arechemically suitable with the liquid phase solutions contemplated inelectrochemical cell 102. All of the membrane and separator materialssuggested or described in this invention may also be employed in thevarious other electrochemical cells designs and methods disclosed inthis application which are non-aqueous or aqueous based.

Microporous separators may also be employed in some electrochemicalsystem options such as microporous PVDF (polyvinylidiene difluoride)based, PTFE (polytetrafluoroethylene), or glass fiber based materials aswell as commercial diaphragms available for the chlor alkali industry.These microporous separators may also be prepared and constructed invarious other plastics or polymers or their combinations that arechemically suitable for the solvent and salts employed inelectrochemical cell 102. In addition, multiple layers may be employedusing one or more separator types. In addition, ceramic based porousseparators, which may be in flexible sheet forms, may be employed, forexample aluminum oxide (alumina) based, silicon oxide based, andzirconium oxide based and their various combinations in addition toboron carbides and the like.

Another suitable membrane separator material, being marketed byCeramHyd, under the trade name CERAPEM, employs an activated boronnitride in a PTFE matrix may also be suitable for some of the variouselectrochemical cells described in this disclosure.

Alternative ceramic based membranes may also be employed as separators,especially those that may conduct and operate at the low temperatures,5° C. to 200° C., for the various electrochemical cells that may be usedin this disclosure. These membranes may be selective in various cationssuch as alkali metal or even hydrogen ions.

Suitable electrochemical separators include commercially available PVDF(polyvinylidene difluoride) filtration material with a 0.1-0.45 micronpore size, available with a thickness of approximately 145 microns thickmay be used. Such as material is manufactured by Meissner anddistributed by Tisch scientific. Lithium ion battery materials, forexample from W. L. Gore and Associates (polytetrafluoroethylene PTFEbased), may also be used. Other lithium battery battery separatormaterials may include inorganic compounds tomprovide dimensionalstability The selection of the separator is based on the compatibilityof the separator or membrane with the solvent(s) selected and stabilityto the anode reaction product.

Other separator materials that may be used in the electrochemical cellinclude:

Polymeric porous separators for lithium ion batteries and filtrationprocesses

-   -   a. PVDF, PTFE, Polyolefin, HDPE, PEEK (polyether ether ketone),        nylon    -   b. Composite polymer matrix with inorganic particle and fiber        fillers    -   c. Fiber (woven polymer) supported polymers

Inorganic Filtration Materials

-   -   a. Ceramics comprising silica, alumina, titania, and zirconia in        a woven or nonwoven form, with and without binders    -   b. Partially sintered glass fiber and and ceramic materials

Perfluorinated Ionomers

-   -   a. Nafion® brand perfluorinated sulfonic acid based membranes        and cation exchange related membrane materials    -   b. Composite perfluorinated ionomers which incorporate inorganic        particles or fibers in the ionomer matrix

Combination hybrid Organic-Inorganic membranes having an inorganicwithin a polymer matrix Partially fluorinated and hydrocarbon-basedionomers (e.g., PEEK-S)

Solid State Ion Conductors and Composites Including these Materials

-   -   a. E.g., ceramic membrane composed of boron nitride with PTFE        matrix

Hydrocarbon based membranes, which may be fabricated from ion exchangeresin materials

The electrochemical cells described herein may be independentlyconfigured in three ways: Three major flow configurations may be used:

-   -   Flow-in (flow inside a 3D electrode structure parallel to the        separator)    -   Flow-by (flow in a plenum/open mesh along the 3D electrode        surface parallel to separator)        -   flow along either the side facing the separator or the side            facing the back plate    -   Flow-thru (flow through the electrode, perpendicular to        separator)        -   flow towards and away from separator

Referring once again to FIGS. 1 and 12, electrochemical reduction cell130, also referred as the anolyte recovery electrochemical cell, may besimilar to electrochemical cell 102. Electrochemical reduction cell 130may include a first region and a second region. First region and secondregion may refer to a compartment, section, or generally enclosed space,and the like without departing from the scope and intent of the presentdisclosure. First region 116 may include a cathode. Second region 118may include an anode. Electrochemical reduction cell 130 may reduce ahalogen or trihalide anion 115 to HX 132 at the cathode and oxidizewater 134 at the anode, producing oxygen (O₂) and liberating hydrogenions (H⁺) to be transferred across the membrane of the electrochemicalreduction cell 130 to generate the HX 132.

Electrochemical reduction cell 130 may produce an acid, such as HX, thatmay be used to acidify oxalate and allow the recycle of the halogen ormultivalent material for reuse to electrochemical cell 102. There areseveral ways to configure the electrochemical cell 130. A two regionelectrochemical reduction cell, including a catholyte region and ananolyte region separated by a cation ion exchange membrane may be used.The anode reaction may be the oxidation of water in an inorganic acidproducing hydrogen ions and oxygen. The hydrogen ions may then passthrough the membrane into the cathode compartment. In the cathodecompartment, the feed of halogen, such as Br₂, may then be reduced atthe cathode to bromide ions (Bo, and then combine with the hydrogen ionsto produce HBr. The cathode reaction may require a high surface areastructure to efficiently convert the X₂ halogen or X₃ ⁻ halide anion tothe HX acid. An aqueous or non-aqueous catholyte with the addition ofwater may also be used. For instance, the non-aqueous solvent from theanode region 118 of electrochemical cell 102 may be fed directly intoelectrochemical cell 130 for bromine reduction, or the bromine might beseparated from the anolyte of electrochemical cell 102 and introduced tothe catholyte of electrochemical cell 130 for reduction. The HX may thenpassed on to the next reactor the acidification reactor 1030 to acidifyand convert alkali metal oxalate or tetraalkylammonium oxalate to oxalicacid.

Referring once again to FIG. 2, electrochemical cell 210, also referredas an electrochemical acidification cell, is configured to convertoxalate to oxalic acid. Hydrogen ions may be generated in the anode, oranolyte region 118 and pass through a central ion exchange region 212bounded by two cation ion exchange membranes 214, 216. The M-oxalatesolution is passed through the ion exchange compartment 212 where theM-cations are exchanged for the hydrogen ions, producing oxalic acid,and the M-cations pass through the adjoining second cation membrane 214into the catholyte region 116. In the catholyte region, the X₂ or X₃ ⁻,such as bromine or tribromide, is reduced at the cathode 122, formingX⁻, such as bromide, which combines with the M-cations to form an MXreduced product. The MX 117 may then be recycled to electrochemical cell102.

Electrochemical cell 210 may include three regions, a first region 116such as a catholyte region, a second region 118 such as an anolyteregion and a third region 212 such as central ion exchange region by twocation exchange membranes on each side. The second region 118 includesan anode 124 suitable to oxidize water. In a preferred implementation,the anode 124 is a titanium anode having an anode electrocatalystcoating which faces the adjacent cation exchange membrane 216. The firstregion 116 includes a cathode 122 suitable to reduce water and togenerate an alkali metal hydroxide.

In a preferred implementation, hydrogen ions (H⁺) or protons aregenerated in the second region 118 a potential and current are appliedto the electrochemical cell 210. The hydrogen ions (H⁺) or protons passthrough the adjacent cation exchange membrane 216 into the central ionexchange region 212. An alkali metal oxalate, or tetraalkylammoniumoxalate, stream is preferably introduced to the electrochemical cell 210into the bottom of the central ion exchange region 212, where thehydrogen ions (H⁺) or protons displace the ions (e.g., lithium ortetraalkylammonium ions) in the product stream to acidify the stream andproduce the oxalic acid 144. The displaced cations may pass through theadjoining cation exchange membrane 214 into the first region 116 tocombine with hydroxide ions (OH⁻) formed from water reduction at thecathode 122 to form a hydroxide, such as lithium or tetraalkylammoniumhydroxide.

The central ion exchange region 212 may include a plastic mesh spacer(not shown) to maintain the dimensional space in the central ionexchange region 212 between the cation exchange membranes 214, 216. Inan embodiment, a cation ion exchange material may be included in thecentral ion exchange region 212 between the cation exchange membranes212, 214. It is contemplated that the cation ion exchange material mayincrease electrolyte conductivity in the ion exchange region solution.

The second region 118 generally may include an anode feed stream thatincludes an acid anolyte solution, such as a sulfuric acid solution, oran HX solution, and may produce a gaseous oxygen product 222. Adeionized water source 220 and an acid make-up source may maintainanolyte acid strength and volume for the anode recycle loop, not shown.

The first region 116 may include a cathode feed stream that includeswater and may include an alkali metal hydroxide that circulates throughthe catholyte recycle loop. The reaction products, which may include analkali metal hydroxide and hydrogen gas, may exit the first region 116.

It is contemplated that electrochemical cell 210 may include a catholytedisengager configured to process a cathode exit stream into a hydrogenstream, a catholyte recycle stream, and a catholyte overflow streamwhich may include hydroxide. The hydrogen stream may be vented from thecatholyte disengager. The catholyte recycle stream preferably includesan alkali metal hydroxide, such as lithium hydroxide, ortetraalkylammonium hydroxide. The catholyte stream may have a deionizedwater source to control the concentration of the hydroxide.

It is contemplated that electrochemical cell 210 may include a varietyof characteristics to improve performance. High surface area cathodestructures are preferred. Carbon materials such as high surface areacarbon and graphite felts may be employed for the reduction of thehalogen. The cathode may include preferred void volume, ranging from 30%to 98%, a specific surface area from 2 cm²/cm³ to 500 cm²/cm³ or higher.The surface area also can be defined as total area in comparison to thecurrent distributor/conductor back plate, with a preferred range of 2×to 1000× or more.

For the anode reaction with the generation of oxygen, electrocatalyticcoatings of precious metals, such as platinum, and precious metal oxidessuch as ruthenium and iridium oxides and their combinations as metalsand oxides on valve metal substrates such as titanium, tantalum, orniobium are suitable. As described herein, high surface area anodestructures may also be used.

Dilute inorganic acids may be used as the anolyte, such as HX acids orsulfuric acid or phosphoric acid with the addition of water into theanolyte compartment to compensate for water losses as needed.

Referring once again to FIG. 3, anion exchanger 140, also referred as anacidification and separation unit, is configured to recycle salt toelectrochemical cell 102 and to acidify oxalate salt to oxalic acid 144.In one embodiment, anion exchanger 140 may include an anion exchangecolumn. Oxalate salt 113 in solution may be passed through the columnand oxalate salt may adsorb to the column material, causing anotheranion to desorb and combine with the cation(s) from the oxalate to formsalt or salts. The anion would typically be the conjugate base of anacid. When an acid solution is introduced to the column, the oxalate maybe desorbed as oxalic acid and the conjugate base of the acid, such asCl⁻, Br⁻, or I⁻ is adsorbed to the column. The overall effect may be toachieve acidification of oxalic acid and separation of the oxalic acidfrom the salt used in electrochemical cell 102. The oxalic acid 144 maythen be utilized as a product or further processed to another chemical.The salt used in the first electrochemical cell may be recycled so theremay be few byproducts of the process.

The separation, acidification, and solvent transfer process of anionexchanger 140 may be effected by a basic anion exchange resin. Anembodiment of the process is illustrated in FIG. 4, which includesabsorbing oxalate ions using a basic anion exchange resin and desorbingthe oxalate with a desired mineral acid. Referring to FIG. 5, a moredetailed series of flow diagrams illustrating the oxalate absorption,water rinsing, regeneration, and solvent rinse steps is shown.

Step 1: The process starts with primary inputs of solvent mix A whichmay be either a single solvent or mixture of solvents, oxalate ions ofthe form M_(n)C₂O₄ where M is a cation that is monovalent or divalent,and X is an anion such as Cl⁻, Br⁻, or I⁻. The input solution may bepassed through a strong base ion exchange resin in the X⁻ form; oxalateis absorbed by the anion exchange resin, liberating X⁻. The effluentrecycle stream may include solvent A and salt M_(n)X_(m).

Step 2: When the ion exchange bed is exhausted and oxalate begins tobreak through the bed, the bed may be drained and rinsed with water.Rinsing may remove solvent A from the resin bed.

Step 3: The bed may be regenerated with an aqueous HX solution ofsufficient concentration to cause the desorption of oxalate ions.Regeneration may result in a mixed stream of oxalic acid and HX inwater.

Step 4: After regeneration, the bed may be drained and rinsed withsolvent A. The process may now be restarted by returning to Step 1.

In this embodiment, the oxalate salt may be removed from one solvent andre-dissolved as oxalic acid in an aqueous phase. This is specificallyuseful coupled with the electrochemical hydrogenation cells 620, 630 ofFIG. 6 which may which require oxalic acid in an aqueous electrolyte.

In a different embodiment, a solvent used in the anion exchange processas the regenerate could be solvent A or another non-aqueous solvent. Inthis embodiment, oxalic acid may be re-dissolved in solvent A or anothernon-aqueous solvent followed by thermal catalytic hydrogenation ofoxalic acid as shown in thermal hydrogenation device 610 of FIG. 6.Catalytic hydrogenation of oxalic acid may be performed in eitheraqueous or non-aqueous solution.

In another embodiment, the oxalate salt may be precipitated from thenon-aqueous phase recovered from electrochemical cell 102 by using acombination of a cation and solvent to give low solubility oxalate salt.This may be described as shown in FIG. 24. After isolation of the saltit may be dissolved in an aqueous solution and acidified with HX. Inorder to recover the MX for reuse, an appropriate solvent may be addedto the aqueous solution of oxalic acid and MX to cause MX precipitation.The MX may be dried and recycled, and a second solvent separated fromthe aqueous phase to recover the second solvent. This may provide oxalicacid in aqueous solution for use in electrochemical hydrogenation cells620, 630 of FIG. 6B and FIG. 6C.

In another embodiment, the oxalate salt may be precipitated from thenon-aqueous phase from electrochemical cell 102 by using a combinationof a cation and solvent to give a low solubility oxalate salt. Afterisolation this salt may be dissolved in an aqueous solution andacidified with HX. Using liquid-liquid extraction, oxalic acid may beextracted into a second phase, as shown in FIG. 23. The extractionsolvent may be separated from the oxalic acid and recovered, leavingoxalic acid to be re-dissolved in an aqueous solution. The MX left inthe aqueous phase may be dried and recycled, for example toelectrochemical cell 102.

Oxalic acid may be recovered as a saleable product or may be furtherreduced to more reduced C₂ or C₄ chemicals. The methods of reduction mayinvolve either thermal catalytic hydrogenation or electrochemicalreduction as shown in FIGS. 6A, 6B and 6C.

It is contemplated that hydrogenation device 150 as depicted in FIGS.1-3 and 10-14 may be implemented as one of devices 610, 620, 630 asshown in FIGS. 6A, 6B, 6C, and 16. Referring specifically to FIG. 6A,thermal catalytic hydrogenation device 610 may be configured to retainoxalic acid in a non-aqueous solvent through the anion exchanger 140.Oxalic acid may also be in an aqueous solution. It may then behydrogenated to a more reduced chemical such as glyoxylic acid, glycolicacid, glycolaldehyde, ethylene glycol, ethanol, acetaldehyde, aceticacid, ethane, ethylene, or glyoxal via the addition of heat, pressure,and/or introduction of a hydrogenation catalyst. C₄ chemicals may alsobe produced. For instance, oxalic acid in propylene carbonate might bepumped into a high-pressure reactor, pressurized with H₂, and heated inthe presence of a supported hydrogenation catalyst. Ethylene glycol, orglycolic acid, may then be recovered upon completion of the reaction.

The overall equation for hydrogenation device 610 for C₂ products is:

H₂O₂O₄ +zH₂→H_(x)C₂O_(y) +zH₂O

For hydrogenation device 610, catalysts may include cobalt, copper,ruthenium, ruthenium dioxide, cobalt nickel alloys, nickel, Pt groupmetals, rhenium, copper chromite, zinc copper chromite, barium chromite,ammonium copper chromate, zinc chromate, Raney nickel, manganesechromate, and alloys of copper and the other metals listed. Thesecatalysts may be supported on carbon, alumina, silica, diatomaceousearth, pumice, zeolites, or molecular sieves.

Promotors such as trivalent phosphorus compounds, ammonia, andalkylammonium salts may be employed. The operation may be either batchmode or continuous flow mode with either a fixed bed or a fluidized bed.Contact time of the reactant with the catalyst may be greater than 0.1seconds.

The reactant for hydrogenation device 610 may be either oxalic acid, anoxalate salt, oxalic acid dihydrate, or the diester of oxalic acid. TheH₂ pressure may be greater than 10 atmospheres and may be between10-1000 atmospheres. The H₂ concentration may be in excess of thestoichiometric amount required to reduce oxalic acid to ethylene glycol.The temperature may be between 50° C. to 500° C., preferably less than150° C. to avoid thermal decomposition of oxalic acid.

It is contemplated that the oxalic acid carrier may include anon-aqueous solvent such as those which may be used in electrochemicalcell 102. In one embodiment, the oxalate salt will be acidified wherethe solvent could include propylene carbonate or acetonitrile. Thecations liberated from the oxalate salt may be recycled to the catholyteregion of an electrochemical cell, while the oxalate salt is acidifiedto oxalic acid in a non-aqueous stream. A stream comprising oxalic acid,a non-aqueous solvent, with or without a further salt, may be directedto the hydrogenation device 610 for hydrogenation.

The hydrogenation of oxalic acid may take place in water, a non-aqueoussolvent, or in the gas phase. Oxalic acid may also be contacted with analcohol, such as methanol or ethanol or butanol, to form esters toinclude dimethyl oxalate or diethyl oxalate or dibutyl oxalate. Theseesters may then be hydrogenated, which allows for the production ofhigher order products and the recovery of the alcohol.

Hydrogenation of the oxalic acid mono and diesters is well reported inthe literature and is traditionally carried over supported NiO/CuOcatalysts in both gas and in liquid phase. The liquid phasehydrogenation of oxalic acid may take place through a series ofintermediates, as shown in FIG. 15, leading to ethylene glycol.According to this reaction scheme, the hydrogenation of oxalic acidgenerates glyoxylic acid, which may be converted to either glyoxal orglycolic acid, and further hydrogenation of either of these twointermediates generates the glycolic aldehyde, the glycolic aldehyde maybe converted to ethylene glycol.

It is contemplated that the electrochemical hydrogenation cells 620, 630of FIGS. 6B and 6C may be suitable for hydrogenation of oxalic acid toglyoxylic acid. It is further contemplated that thermal catalytichydrogenation device 610 may be suitable for hydrogenation of oxalicacid to glycolic acid as a first possible product or ethylene glycol asa second possible product.

Referring to FIG. 16, a schematic illustrating the components of athermal catalytic hydrogenation system is shown. Thermal catalytichydrogenation system 1600 may be one implementation of hydrogenationdevice 150 of FIGS. 1-3 and FIGS. 10-14. Thermal catalytic hydrogenationsystem 1600 may include a reactor configured for continuous monitoringof a hydrogen uptake rate. Reactor may include a standard 100 mLstainless steel PARR Autoclave 5. The entire vessel of the reactor maybe removed from a stand as a complete assembly for either charging orproduct recovery. The reactor is equipped with a magnetically coupleddrive with a permanent magnet for the inner rotor, to which the stirringshaft is attached. Additionally, a water cooling sleeve attached to thedrive protects the components from excessive heat arising from a head ofthe reactor. The first port, 1 accommodates a safety rupture discintended to release pressure if a critical level is exceeded. Port 2 isa combination port which holds liquid sampling and gas inlet valves. Thesampling valve allows removal of liquid product samples without the needto open the reactor. A dip tube fitted with stainless steel frit at thetip allows extraction of liquid samples while allowing the catalyst toremain in the reactor. The catalyst may then be reused in subsequentreactions. Port 3A is a combination port configured to accommodate apressure gauge and a ⅛″ stainless steel needle valve. Port 3B is asecond combination port accommodating a pressure gage and a ⅛″ stainlesssteel needle valve. The latter is used as a primary gas inlet port forinitially purging and pressurizing the reactor and the port itself isconnected to the volumetric section of the reactor system through a ⅛″stainless steel tube. Port 4 comprises a J-type thermocouple while theremaining two ports can be fitted with a cooling coil for accuratecontrol of the reactor temperature. The cooling coil may also be removedto produce two additional ports. A first additional port may be leftblank while a second additional port, 6 may be fitted with ¼″ on/offvalve used for loading reaction solutions using gas-tight syringes.

For catalyst activation (pre-reduction), the reactor may be charged with5 wt % Ru/C catalyst and 40 mL deionized water. The reactor may bealternately purged with argon 5 times and hydrogen also 5 times. Thesystem 1600 may be pressurized to 800 psi, the reactor heated to thedesired temperature and stirred for 3 hours at stirring rate of 200-300RPM. The reactor may then be cooled to ambient temperature, and withoutopening the reactor, the water may be siphoned out through a dip tube,fitted with 2 mkm stainless still fritted filter.

After catalyst activation (pre-reduction), the reactor may be chargedwith 41.5 gm of 5% aqueous oxalic acid solution using a gas-tightsyringe. To remove dissolved oxygen, the feed solution may be kept in asepta-sealed glass bottle and may be carefully purged with inert gas forat least 30 min before injection into the reactor. The reactor may beflushed 5 times and pressurized with hydrogen to 800 psi, the stirringrate may be set initially to 200 RPM and the reactor heated to desiredtemperature (between 50° C. and 170° C.) over a period of 60 minutes.The pressure may be adjusted to the desired setting, the stirring rateincreased to 800-900 RPM and monitoring of the hydrogen uptake wasinitiated. During the first 6 hours, samples may be taken at 2 hourintervals and hydrogenations were typically continued for 21 hours.

Catalysts employed in the hydrogenation reactions of thermal catalytichydrogenation system 1600 may include Ru/C, Ru/SiO₂, Ru/Al₂O₃, Pd/C, andCu-Chromite. Temperatures may range from approximately 50° C. toapproximately 170° C. Hydrogen may be employed at pressures of about 300psi to about 1500 psi. Stirring rates may range from about 400 RPM toabout 800 RPM. The hydrogenation reactor may be stainless steel, unlinedor Teflon lined, or glass lined. The reactor may also be made ofHastelloy or Elgiloy or other corrosion resistant materials. Startingmaterial concentrations of oxalic acid may range from about 5% by weightto about 50% by weight. Products from the thermal catalytichydrogenation reaction may include mono ethylene glycol, glycolic acid,and acetic acid.

In one exemplary operation, to a container charged with 7.5% by weightof activated (pre-reduced) Ru/C catalyst was added 100 gm of a 25% byweight oxalic acid solution in water. The mixture was subjected tothermal catalytic hydrogenation conditions as described above at atemperature of 75° C., with a stirring rate of 400 RPM and a pressure of1500 psi of hydrogen. After six hours, the reaction was worked up toprovide by weight 76.4% glycolic acid, 6.6% mono-ethylene glycol, and10.5% acetic acid with a total recovered carbon balance of 93.5%.

In another embodiment, the temperature of the hydrogenation may beinitially held at a temperature between 50° C. to 85° C. for a period of5 to 8 hours followed by an increase in temperature to between 110° C.and 150° C. for a period of 2 to 5 hours. At the end of the reactionmonoethylene glycol may be isolated. Initial hydrogenation at a lowertemperature may minimize thermal decomposition of oxalic acid.

In another embodiment, after the reaction mixture has reached a reactiontemperature between 50° C. and 170° C., the oxalic acid may be slowlyadded to the reaction mixture in order to minimize the concentration ofoxalic acid in the reaction mixture.

Referring to FIG. 17, a schematic illustrating a reactive distillationcolumn is shown. Reactive distillation is a process technology with thepotential to simultaneously perform chemical reactions and separationsof product and reactants. The reactive distillation process performed bythe reactive distillation column 1700 may be configured foresterification of oxalic acid with alcohol (1-butanol, ethanol andmethanol) to produce dialkyl oxalate (dibutyl oxalate (DBO), diethyloxalate (DEO), dimethyl oxalate (DMO), and the like.

Reactive distillation column 1700 may include a rectifying zone, areactive zone and a distillation zone. Reactive distillation column 1700may receive oxalic acid and an alcohol, such as butanol. Reactivedistillation column may simultaneously reactive and separate the dibutyloxalate which may then be hydrogenated to mono-ethylene glycol.

Oxalic acid has unique properties. It is highly acidic compared to otherdicarboxylic acids and it is thermally unstable due to the presence ofthe adjacent carboxylic acid groups. Acidity and thermal stability mustbe carefully considered when designing a process to selectivelysynthesize a dialkyl ester and separate it from other chemical species.

Once formed, an oxalic acid diester may then be hydrogenated tomono-ethylene glycol (MEG) with great selectivity and efficiency. Oxalicacid diester may be obtained by condensing oxalic acid with lowmolecular weight alcohols such as methanol, ethanol, propanol,isopropanol, butanol or iso-butanol using an acid. Protic Bronsted acidssuch as H₂SO₄, HCl, H₂PO₄, p-TsOH, and MsOH have been used as the acidcatalysts in conventional esterification chemistry. Esterifications mayalso be catalyzed with solid acids such as Amberlyt-15, Amberlyst-35,Smopex 101, Zeolite-Y, H-USY, Zeolite-X, Zeolite-β, Zeolite Mordenite,Silica-Alumina, Molybdatophosphoric acid hydrate, sulfated zirconia,sulfated SnO₂, sulfated TiO₂, sulfated Nb₂O₅, Tungstated ZrO₂, NafionSiO₂ composite (SAC-13), Mo/ZrO₂, Nb/ZrO₂ etc.

The use of solid acids for esterifications may be advantageous due toits simplicity at a process level. Solid acids may be placed in afixed-bed type system thereby reducing the overall capital cost of theprocess by eliminating a need for a separation of the acid from thereaction mixture. In most of the cases, mineral acids that are used foresterification are lost without recovery due to low concentration, whichin turn increases downstream purification and waste treatment costs.

Both conventional esterification methods (such as: Soxhlet extraction,liquid-liquid extraction, Dean-Stark, in situ drying methods, etc.) aswell as advanced reactive distillation column (RDC) methods may be usedto form oxalate esters. Various alcohols, catalysts, oxalic/alcoholratio, catalyst loading, temperature and other reaction conditions havebeen considered in order to enhance the kinetics, product concentration,and yield.

Bench scale batch reactions of the esterification of oxalic acid withmethanol, ethanol, and butanol using solid acids such as Amberlyst-15and Silica-Alumina may be conducted to determine rate and conditions forthe optimal yield of the esterification. Removal of water may generateoptimal yields and rates. These parameters may be utilized to design thereactive distillation column 1700 for the esterification of oxalic acidwith a solid acid catalyst, which shifts the esterification of dialkyloxalate reactions both chemically and thermodynamically to overcome thetheoretical limits imposed by both chemical and phase equilibria of thehighly non-ideal systems.

Esterification Experiments Diethyl Oxalate (In Situ Drying Agent):

An anhydrous oxalic acid (1 g, 11.1 mmol) was placed in a round bottomflask and was dissolved in anhydrous ethanol (50 mL, 39.45 gm, 85.6mmol). The mixture was stirred at room temperature until the oxalic aciddissolved. Amberlyst 15 hydrogen form (2.00 gm) was added along withmagnesium sulfate (2.5 gm, 20.77 mmol) and a rubber septum used to sealthe flask. The mixture was allowed to stir at 60° C. under a nitrogenfilled balloon. After 2.5 hours, additional magnesium sulfate (2.5 gm,20.77 mmol) was added to the reaction mixture and then stirred for atotal of 4.5 hours. The reaction was cooled and filtered. The crudeliquid reaction mixture was concentrated via rotary evaporationaffording a light brown oil containing a small amount of residualmagnesium sulfate.

Dimethyl Oxalate (Soxhlet):

An anhydrous oxalic acid (12.22 gm, 0.135 mol) was dissolved inanhydrous methanol (110 mL, 86.5 gm, 2.7 mol) in a round bottom flaskand stirred until the oxalic acid was dissolved. Toluene (110 mL) wasadded to the mixture along with p-toluene sulfonic acid (1.28 gm, 6.75mmol). A Soxhlet extractor containing a glass thimble packed withmagnesium sulfate was placed over the round bottom flask. The mixturewas refluxed for 18 hours. At the end of this time, the reaction mixturewas cooled to room temperature and solvent was concentrated via a rotaryevaporation yielding a white solid (13.8 gm, 87% crude yield).

Dimethyl Oxalate (Dean-Stark)

An anhydrous oxalic acid (22.22 gm, 0.25 moles), p-toluene sulfonic acidmonohydrate (2.34 gm, 0.123 moles) and methanol (100 mL, 79.1 gm, 2.47moles) were added to a round bottom flask. The round bottom flask wasattached to a dean-stark apparatus filled with toluene. The reaction wasrefluxed for 18 hours. At the end of this time, the reaction mixture wasconcentrated via a rotary evaporation affording white solid (30.17,95.5% crude yield).

Dimethyl Oxalate (Liquid-Liquid Extractor):

An anhydrous oxalic acid (66.68 g, 0.74 moles), methanol (600 mL, 474.6g, 14.81 moles) and deionized H₂O (290 mL) were added to a body of theliquid-liquid extractor. P-toluene sulfonic acid monohydrate (27.06 gm,0.142 moles) was added to a reactor body along with toluene (100 mL).Toluene (500 mL) may also be placed in the round bottom flask of theliquid-liquid extractor and heated in a 150° C. oil bath. The reactionwas left to stir for several hours. The organic solution wasconcentrated via a rotary evaporation affording a white solid (44.3 gm,51% crude yield).

Note on Catalyst Activation (Silica-Alumina):

Silica alumina (50 gm) was placed in 1M ammonium chloride (250 mL) andmay be stirred for six hours at room temperature. The silica-alumina wasfiltered off with a fritted Buchner funnel, washed with deionized H₂O,and dried for several hours. Around 8.65 gm was left to calcine for 5.5hours under argon gas at 450° C. in a tube oven. After cooling to roomtemperature, the silica-alumina may be placed in a vacuum oven at 60° C.for 45 minutes prior to use.

Reactive Distillation

Reactive distillation involves the simultaneous reaction as well asseparation of the reaction components using a catalyst at proper systemtemperature. Esterification is an exothermic process and hence lot ofheat is generated during the reaction. In conventional process, thismajority of the heat is extracted using heat transfer methods and notutilized comprehensively. In RDC, the heat is utilized internally toheat the reaction components in order to carry out separationsimultaneously. This advanced simultaneous process reduces thermalenergy cost considerably. Based on the physical and chemical propertiessuch as boiling point, stability, miscibility, affinity, reactivity ofthe reactants and products, RDC methods of producing dibutyl oxalate(DBO) and diethyl oxalate (DEO) have been designed and tested.

Reactive Distillation of Dibutyl Oxalate

As shown in FIG. 17, oxalic acid in 1-butanol solution at 95° C. orhigher is fed into a location at the upper portion of the column, andthe rest of 1-butanol (total of 1:5 molar ratio of oxalic acid tobutanol) is fed at a location of the lower portion of the column closeto the column bottom at a temperature of 100° C. to 130° C. The columnis packed with solid acid catalyst in the middle section, the lower andupper sections of the column are packed with structural packing withoutcatalytic reactivity for separations purpose only, identified asrectifying and distillation zones.

Esterification happens in the middle of the column. Water and unreactedbutanol are recovered at the top of the column in a decanter, thebutanol in the top phase is then recycled back for furtheresterification. The bottom stream has a dibutyl oxalate concentration of46% wt to 75% wt, the rest of the mixture is butanol along with a minoramount of water, the product stream may be further separated to yieldhigher purity dibutyl oxalate for subsequent use.

Reactive Distillation of Diethyl oxalate

Oxalic acid in ethanol (EtOH) solution at 79.4° C. may be fed intoproper location at the upper portion 1710 of the column and the rest ofethanol (total of 1:5 molar ratio of OA to EtOH) may be fed at a properlocation of the lower portion of the column 1720 at a temperature of80.5° C. The column may be packed with acid catalyst in the middlesection 1730, the lower and upper sections 1710, 1720 of the column arepacked with structural packing without catalytic reactivity forseparations purpose only.

Esterification happens in the middle of the column, 1730, the reactivezone. Unreacted ethanol is recovered at less than 93% weight at the topof the column 1710 (lower than the azeotrope composition with water), itis then dried and recycled back for further reaction. The bottom stream(product stream) has a diethyl oxalate concentration of 87% weight, therest is water and a minor amount of ethanol, the stream may be furtherseparated to yield higher purity diethyl oxalate for subsequent use.

TABLE Comparison of the esterification rate of batch and RDC method:Conventional batch method RDC method Rate of dialkyl ester 30-150gram/hour-liter 150-400 gram/hour-liter formation

Due to the efficient removal of water in RDC method, the rate may bemuch higher than that of conventional batch method.

The reactive distillation column 1700 may be designed in a way that itcan separate reactive mixtures involving azeotropes to a large extent.Such separations may be difficult to achieve by conventional“distillation after reaction” mechanism where reactions are fullycontrolled by the equilibrium limit and phase behavior is controlled byazeotrope properties.

The heat released by esterification of oxalic acid may be used forvaporizing water without the need for heat exchange equipment andheating and cooling resources, and without thermal resistance.

Solid acid Amberlyst and Zeolites catalysts may be used, instead ofH₂SO₄ or other liquid acids which may be lost in the process resultingin additional waste treatment costs. Solid acid catalysts may be packedin a bed and have a lifetime of several years.

The esterification reactions may occur at atmospheric pressure andtemperature ranges from 100° C. to 160° C., depending on the catalystused.

The oxalate esters obtained from reactive distillation may be used insubsequent processes. For example, the esters may be reduced to ethyleneglycol via thermal catalytic hydrogenation.

Referring once again to FIGS. 6B and 6C, oxalic acid may beelectrochemically reduced to C₂ and C₄ products at the cathode 122 ofthe electrochemical cell 620, 630. Various anodic reactions thatliberate available H+ may be employed. As shown in FIG. 6B,electrochemical cell 620 may be configured for water oxidation to H⁺ andO₂ if a benign side product is desired. This is given by the equationfor C₂ products:

H₂O₂O₄→H_(x)C₂O_(y) +zO₂

As shown in FIG. 6C, electrochemical cell 630 may be configured for HXoxidation to a halogen and H⁺ if a halogen is desired as the product.This is given by the equation for C₂ products:

H₂O₂O₄+2zHX→H_(x)C₂O_(y) +zH₂O+zX₂

Similarly, the oxidation of other organic and inorganic species may beemployed as the anolyte reaction and are not limited to thesevariations.

As shown in FIGS. 6B and 6C, electrochemical cells 620, 630 may havecathodes that may include and are not limited to Pb, C, graphite,semiconductors, In, Sn, Zn, Cd, Hg, amalgams, Bi, Ga, alloys containingPb, In, Sn, Zn, Cd, Hg, Bi, Ga, bimetallics containing Hg with anotherconductor, or other combinations of bimetallics, and metal carbides. Thecatholyte may include homogeneous catalysts. Homogeneous catalysts mayinclude aromatic heterocyclic amines and may include, but are notlimited to, unsubstituted and substituted pyridines and imidazoles.Substituted pyridines and imidazoles may include, but are not limited tomono and disubstituted pyridines and imidazoles. For example, suitablecatalysts may include straight chain or branched chain lower alkyl(e.g., C1-C10) mono and disubstituted compounds such as2-methylpyridine, 4-tertbutyl pyridine, 2,6 dimethylpyridine(2,6-lutidine); bipyridines, such as 4,4′-bipyridine; amino-substitutedpyridines, such as 4-dimethylamino pyridine; and hydroxyl-substitutedpyridines (e.g., 4-hydroxy-pyridine) and substituted or unsubstitutedquinoline or isoquinolines. The catalysts may also suitably includesubstituted or unsubstituted dinitrogen heterocyclic amines, such aspyrazine, pyridazine and pyrimidine. Other catalysts generally includeazoles, imidazoles, indoles, oxazoles, thiazoles, substituted speciesand complex multi-ring amines such as adenine, pterin, pteridine,benzimidazole, phenonthroline and the like.

For bromine and iodine anode chemistry, carbon and graphite may beparticularly suitable for use as anodes in electrochemical cells 620,630. Polymeric bonded carbon sheets may also be used. For otherchemistries, carbon, cobalt oxides, stainless steels, their alloys andcombinations may be employed as well as coatings of precious metaloxides such as ruthenium and iridium oxides, as well as platinum andgold and their combinations as metals and oxides on valve metalsubstrates such as titanium, tantalum, or niobium.

A desired salt in the catholyte region 116 of electrochemical cells 620,630 may include either HBr, HCl, HI, H₂SO₄, bromide, chloride, orsulfate salts where the cation is sodium, potassium, ammonium,tetraalkylammonium, or another single or divalent cation. Concentrationsof salts may range from mM to M. A desired salt in the anolyte regionmay include either HBr, HCl, HI, H₂SO₄, bromide, chloride, or sulfatesalts where the cation is sodium, potassium, ammonium,tetraalkylammonium or another single or divalent cation. Theconcentration may range from mM to M. The anodic chemistry may also beoperated in the gas phase. In this embodiment, anhydrous HBr or HCl gasanolyte may be used as well as water vapor.

In a preferred embodiment, the solvent may be water with concentrationsof oxalic acid near saturation levels of about 12% by weight. Thesolvent may also be a variety of non-aqueous solvents with specificallyadded quantities of water. These non-aqueous solvents could include butare not limited to propylene carbonate, ethylene carbonate, dimethylcarbonate, diethyl carbonate, dimethylsulfoxide, dimethylformamide,acetonitrile, acetone, tetrahydrofuran, N,N-dimethylacetaminde,dimethoxyethane, diethylene glycol dimethyl ester, butyrolnitrile,1,2-difluorobenzene, γ-butyrolactone, N-methyl-2-pyrrolidone, sulfolane,1,4-dioxane, nitrobenzene, nitromethane, acetic anhydride, and ionicliquids. Oxalic acid may be soluble in the solvent chosen. In oneembodiment, oxalic acid in propylene carbonate with the appropriate saltmay be used as the catholyte.

A preferred oxalic acid concentration may range from 1 mM to about 12%by weight in aqueous solution. The solubility limit of oxalic acid maybe increased by using solvents other than water. The solubility limitmay also be increased by increasing the temperature of the reactionand/or through the use of electrolytes that have a salting effect onoxalic acid. These include thiocyanates, perchlorates,tetrafluoroborates, and hexafluorophosphates.

Generally, the solvent may be the same in both the catholyte region 116and anolyte region 118 of electrochemical cells 620, 630. However, incertain embodiments, the solvent used in the catholyte region 116 andanolyte region 118 may differ. If a halogen is produced in the anolyteregion 118 of electrochemical cell 630, the solvent of choice may bestable in the presence of Br₂, Cl₂, or I₂.

In the catholyte region 116, the pH may depend on the concentration ofoxalic acid and the electrolyte salt or acid employed. In general, thepH may range from 0 to 5. In the anolyte region 118, the pH may dependon the concentration of the electrolyte acid employed. In general, thepH may range from 0 to 5.

The temperature used may depend on the solvent chosen. For aqueoussolution, the preferred temperature range may be 5° C. to 80° C. Lowerand higher temperature ranges may be employed by using various solvents.A catholyte cross sectional area flow rate range may be 2-3,000 gpm/ft²or more (0.0076-11.36 m³/m²). A flow velocity range may be 0.002 to 20ft/sec (0.0006 to 6.1 m/sec).

Electrochemical cells 620, 630 may include zero-gap, flow-by, andflow-through designs with a recirculating catholyte electrolyte withvarious high surface area cathode materials. Also flooded co-currentpacked and trickle bed designs with the various high surface areacathode materials may be employed for the electrochemical cells 620,630. Bipolar stack cell designs, high pressure cell designs and filterpress, zero gap designs with gas phase anodic chemistries and eitheraqueous or non-aqueous cathodic chemistry may be employed for theelectrochemical cell 620, 630.

In one embodiment, the catholyte may include oxalic acid, a solvent, anda salt, with a gas phase HBr anolyte. The cathode and anode materialsmay be in direct contact with the membrane and there may be less than afew millimeters of depth to the anode or cathode region. High surfacearea of the anode and cathode may be achieved through micro andnano-structuring of the electrode materials. Mixed Phase—Gas phaseanodic chemistry with aqueous phase or non-aqueous phase cathodicchemistry may also be implemented.

The cathode/anode electrodes may include a preferred void volume,ranging from 30% to 98% and a specific surface areas from 2 cm²/cm³ to500 cm²/cm³ or higher. Surface areas also may be defined as total areain comparison to the current distributor/conductor back plate, with apreferred range of 2× to 1000× or more.

Cation ion exchange type membranes may be preferred, especially thosethat have a high rejection efficiency to anions, for exampleperfluorinated sulfonic acid based ion exchange membranes such as DuPontNafion brand unreinforced types N117 and N120 series, more preferredPTFE fiber reinforced N324 and N424 types, and similar related membranesmanufactured by Japanese companies under the supplier trade names suchas Flemion.

Other multi-layer perfluorinated ion exchange membranes used in thechlor alkali industry may have a bilayer construction of a sulfonic acidbased membrane layer bonded to a carboxylic acid based membrane layer,which efficiently operates with an anolyte and catholyte above a pH ofabout 2 or higher. These membranes may have much higher anion rejectionefficiency. These are sold by DuPont under their Nafion trademark as theN900 series, such as the N90209, N966, N982, and the 2000 series, suchas the N2010, N2020, and N2030 and all of their types and subtypes.

Hydrocarbon based membranes, which are made from of various cation ionexchange materials may also be used if the anion rejection is not ascritical, such as those sold by Sybron under their trade name Ionac, ACGEngineering (Asahi Glass) under their Selemion trade name, and TokuyamaSoda among others on the market.

Microporous separators may also be employed in some system options suchas microporous PVDF (polyvinylidiene difluoride), PTFE(polytetrafluoroethylene), or glass fiber based materials as well ascommercial diaphragms. Other separators as describe elsewhere herein mayalso be used.

Referring to FIG. 18, a method 1800 for conversion of carbon dioxide tooxalate, oxalic acid and oxalic acid reduction products is shown.

Referring to FIG. 22, a method 2200 for purifying an oxalate salt isshown. Method 2200 may begin with an oxalate salt, such astetrabutylammonium oxalate or other oxalate salt in a non-aqueousaprotic solvent, such as acetonitrile, is received as a startingmaterial. The oxalate salt may be purified by reacting the oxalate saltwith a metal ion (MX₂), optionally dissolved in a second solvent(solvent A), to form a weakly soluble, or insoluble complex (M-Oxalate).For example, metal ions such as Mg, Ca, Zn, Mn, Ni, Fe, and Cu may beemployed. The mixture may be filtered to yield the solid M-Oxalate and asolution of salt, such as tetraalkylammonium halide, in solvent or amixture of solvents. The salt solution and solvent(s) may be recycled.The solid M-Oxalate may be treated with acid HX and solvent or a solventmixture (solvent NB) to yield oxalic acid and salt MX. Oxalic acid maythen be purified from the solution. Salt MX and solvent or solventmixture (solvent A/B) may be recycled.

In another embodiment, an oxalate salt solution may be electrochemicallyacidified. Representative electrochemical acidification cells have beendiscussed previously and are illustrated in FIGS. 7, 8, 9A-C, and 23.

In another embodiment, an oxalate salt may be purified through the useof an ion exchange column, such as an anion exchange column, as shown inFIG. 26. An oxalate salt, such as a tetraalkylammonium oxalate, in anon-aqueous aprotic solvent, such as acetonitrile, and optionallytetraalkylammonium halide may be flowed onto an ion exchange column towhich the oxalate dianion adheres. Oxalate salt solution may be flowedonto the column until oxalate is detected flowing off the column,indicating column saturation. Tetraalkylammonium halide and solventflowing off the column may be recovered and recycled, for example foruse in an electrochemical carbon dioxide reduction cell 102 in FIG. 1.After oxalate salt has been adsorbed onto an ion exchange column, asolution of acid, such a HX, may be flowed onto the column. The acid mayconvert the oxalate salt to oxalic acid and oxalic acid may flow out ofthe column with the solvent and unreacted acid. The oxalic acid and acidHX may then be separated, with the HX being recycled, and oxalic acidbeing isolated or being reacted to form other products, such as furtherreduced two-carbon products.

In another embodiment, an oxalic acid and tetraallkylammonium halidesolution in a non-aqueous aprotic solvent, such as acetonitrile, may bepurified through solid sorbent amine extraction. Solid-phase columnmaterials may comprise Dowex MWA-1, Amberlite IRA-910, Amberlite IRA-35,Reillex 425 or similar materials. An oxalic acid solution in anon-aqueous aprotic solvent, such as acetonitrile, and optionallytetraalkylammonium halide may be flowed onto a solid sorbent aminecolumn to which the oxalic acid adheres. Oxalic acid solution may beflowed onto the column until oxalic acid is detected flowing off thecolumn, indicating column saturation. Tetraalkylammonium halide andsolvent flowing off the column may be recovered and recycled, forexample, for use in an electrochemical carbon dioxide reduction cell 102of FIG. 1. After oxalic acid has been adsorbed onto a solid sorbentamine column, forming a solid sorbent amine-oxalate salt, a solution ofamine base may be flowed onto the column. The base may convert the solidsorbent amine-oxalate salt to soluble amine-oxalate salt and the solubleamine-oxalic acid salt may flow out of the column. The oxalic acid andsoluble amine then be separated, for example through heating, with theamine being recycled and oxalic acid being isolated or being reacted toform other products, such as further reduced two-carbon products.

In another embodiment, an oxalic acid and tetraalkylammonium halidemixture may be purified through chromatography. The mixture may beflowed onto a chromatographic medium, such as a hydrophilic medium or ahydrophobic medium. Suitable chromatographic media include silica gel,alumina, polymers, reverse phase silica gel, and related chromatographicmedia. The oxalic acid and tetraalkylammonium halide mixture may beflowed onto the chromatographic medium in solution, or the mixture maybe combined with the chromatographic medium as a solid. After themixture has been flowed onto the chromatographic medium, or combinedwith the chromatographic medium, a solvent, or mixture of solvents, maybe flowed onto the medium to separate the oxalic acid from thetetraalkylammonium halide. Suitable solvents include water, methanol,ethanol, 1-propanol, isopropanol, acetonitrile, hexane, petroleum ether,diethyl ether, formic acid, acetic acid, ammonia, and triethylamine. Theseparated oxalic acid may be further reduced to two carbon products, andthe tetraalkylammonium halide may be recycled, for example for use in anelectrochemical carbon dioxide reduction cell.

In another embodiment, an oxalic acid and tetraalkylammonium halidesolution in a non-aqueous aprotic solvent, such as acetonitrile, may bepurified through nano-filtration. Two different nano-filtration methodsmay be employed. Referring to FIG. 19, a method 1900 may employnano-filtration that may reject oxalic acid and may allowtetraalkylammonium halide in solvent to pass through the filter. Theresulting permeate stream may be recycled. The reject stream of oxalicacid in solvent may be sent to distillation to remove the solvent, whichmay be recycled, and yield purified oxalic acid. The purified oxalicacid may be further processed to yield other products such as othertwo-carbon containing compounds. Suitable nano-filtration membranes aresolvent stable membranes, such those manufactured by Evonik under thetrade name of DuraMem and PuraMem, which also come in differentmolecular weight cutoffs (i.e., 150, 200, etc. in Daltons) which mayalso improve the selected separations. The pH adjustment of the solventsolution may also have a pH range where the separation selectivity isalso improved, with the addition of excess HX to the solution. Inanother embodiment, if the ACN is replaced by water, the salts may alsobe separated using nano-filtration membranes that are suitable for usein aqueous solutions.

Referring to FIG. 20, a method 2000 may employ nano-filtration that mayreject tetraalkylammonium halide and may allow passage of oxalic acid.The reject stream containing tetraalklyammonium halide in solvent may berecycled. The permeate stream containing oxalic acid may be sent todistillation to remove the solvent, which may be recycled, and yieldpurified oxalic acid. The purified oxalic acid may be further processedto yield other products such as other two-carbon containing compounds.

Referring to FIG. 21, a method 2100 for purifying an oxalic acidsolution containing tetraalkylammonium halide through amine extractionis shown. A solution of oxalic acid in a non-aqueous aprotic solvent,such as acetonitrile, may be treated with an amine, such as atrialkylamine to form an amine-oxalate salt. An amine-oxalate salt mayprecipitate from solution or may form a two phase liquid solution.Addition of an amine salt immiscible solvent may optionally be added toachieve precipitation or phase separation. The amine salt may then befiltered or the two liquid phases may be separated to provide a solutionof tetraalkylammonium halide for recycling and an oxalic acid-aminesalt, which may be a solid or may be in solution. The oxalic acid-aminesalt may then be heated to provide purified oxalic acid, which may beused in subsequent reactions, and amine, which may be recycled.

In another embodiment, an oxalic acid solution containingtetraalkylammonium halide may be purified by liquid-liquid extraction inan extractor apparatus. In this embodiment, either the oxalic acid orthe tetralalkylammonium halide or other salt may have differingsolubility in the different solvents employed. For the case where oxalicacid may have higher solubility in a second solvent, the oxalic acidconcentration will increase in the second solvent and decrease in theinitial solution. This may leave the tetralkylammonium halide salt inthe solvent of the initial solution which may be recycled. A series ofextractor apparatuses may be used to achieve the desired purity. Forexample, counter-current extraction or dropping counter-currentextraction may be employed.

Referring again to FIG. 18, once purified oxalic acid has been obtainedit may be used in further chemistry. For example, the oxalic acid may bereacted with alcohols to form the diester which can then be reduced toform mono-ethylene glycol. Alternatively, oxalic acid may be directlyreduced via thermal catalytic hydrogenation to form glycolic acid, or toform mono-ethylene glycol. In addition, oxalic acid may beelectrochemically reduced to form glyoxylic acid.

As shown in FIG. 18, halide or trihalide anion formed during theelectrochemical reduction of carbon dioxide may be recycled throughthermal, catalytic, or electrochemical reduction systems. For example, astream of halogen may be reacted with a stream of hydrogen to form HXand heat. Once the halogen and hydrogen streams are mixed an ignitionsource would initiate the reaction. Alternatively, halide or trihalideanion may be reacted with hydrogen in the presence of a catalyst to formhydrogen halide and heat. Catalysts such as Pt, Pd, Rh, Ru, Ni, Ir, andother homogeneous or heterogeneous hydrogenation catalysts may be used.Heat from the reaction of hydrogen and halide or trihalide anion may becaptured and used for energy production or to provide heat for otherprocesses. As illustrated in FIG. 25, an electrochemical cell may beused to reduce halide or trihalide anion to HX. Finally, halide ortrihalide anion may be reacted in a fuel cell to provide HX as well aselectrical energy, which may be used in the electrochemical reduction ofcarbon dioxide.

Referring to FIG. 28, electrochemical cell 2800 for producing oxalatefrom the reduction of carbon dioxide in a non-aqueous solvent inaccordance with an another embodiment is shown. An acetonitrile (ACN)solution with a dissolved conductive salt, for example TBABr, may beintroduced into a thin central flow channel or compartment, such thatall of the flow may be evenly distributed in width and height from theflow channel into the adjoining anolyte and catholyte regions containingthe anode and cathode electrode structures respectively. The centralflow channel may comprise a material, such as ionically conductivematerials that may include ion exchange beads or inert nonconductivematerials with a high open area such as plastic mesh screens, plasticbeads, and the like. Advantageously, the flow channel may be kept openand preferably kept dimensionally stable in width or thickness throughthe height of the flow channel. A separator may be used on either sideof the flow channel to help provide the flow resistance required to havean evenly distributed flow into the anolyte and catholyte regions. Theseparator may be a porous material with a small pore size in the rangeof 0.01 to 5 microns with an open area in the range of 20 to 80%. Theseparator may be made from an inert material, such as a plasticmaterial. Plastic material may include PVDF (polyvinylidienedifluoride), HDPE (high density polyethylene), PP (polypropylene), orPTFE (polytetrafluoroethylene). The separator may also be made of an ionconducting material. Ion conducting materials may include ion exchangematerials or membranes, such as sulfonated polystyrene, cation ionexchange sulfonated tetrafluoroethylene materials sold under the tradename of Nafion, as well as hydrocarbon based cation ion exchangematerials sold under the trade names of Selemion, Flemion, Neosepta, andthe like.

The use of the thin flow channel in this electrochemical cell design mayallow for an alternative method for controlling a bulk flow of thesolvent and salt into the cell 2800 which may not be possible when usingjust a single separator between the anolyte and catholyte regions andfeeding in the required solvent into the anolyte and catholyte regionsseparately. The use of porous separators may allow a non-uniform bulkflow distribution from the anolyte to catholyte region, or vice versa,because of pressure differentials between the anolyte and catholyteregion flow loops. The electrochemical cell 2800 may be employed toprevent or minimize any unwanted potential bulk flow from the anolyte tocatholyte and vice versa.

The electrochemical cell catholyte loop may include a pumpedrecirculating catholyte solution where carbon dioxide is dissolved intothe ACN-TBABr solution and the carbon dioxide may be reduced on a highsurface area cathode structure. The high surface cathode structure mayincorporate a cathode current distributor. Cathode materials includetransition group metals and alloys, such as stainless steel 316 ornickel as examples. The oxalate formed at the cathode may then overflowthe catholyte disengager as an ACN solvent containing TBA₂Oxalate andany excess or unreacted TBABr. The catholyte product may then beprocessed in the next unit operation where the oxalate is separated asoxalic acid from the TBABr.

The electrochemical cell anolyte loop may include a pumped recirculatinganolyte solution where the dissolved bromide ion in the ACN-TBABrsolution may be oxidized at the high surface area anode structure tobromine (Br₂). The formed bromine may react with any excess TBABr, suchthat the bromide ion may couple with the formed bromine to form atribromide complex, such as TBABr₃. The high surface anode structure mayincorporate an anode current distributor. Anode materials include carbonmaterials such as carbon and graphite, which may be in the form offelts, needled felts, or woven forms. These carbon based materials mayhave catalysts impregnated into and onto the surfaces of the highsurface area carbon structure includes platinum group metals and theiroxides, mixtures, and alloys, such as gold, platinum, ruthenium dioxide,iridium oxide, and the like that preferably may be chemically resistantto the anode bromine formation chemistry and may help to promote orcatalyze the oxidation of bromide to bromine. Other suitable anodematerials may be valve metals, such as titanium, niobium, and tantalumhaving an electrocatalyst surface coating of the various precious metalgroup metals and their oxides, mixtures, and their alloys. The TBABr₃formed at the anode may then overflow the anolyte disengager as an ACNsolvent containing TBABr₃ and any excess or unreacted TBABr. The anolyteproduct may then be processed in the next unit operation where theTBABr₃ may be reacted with organics to form brominated hydrocarbons, orreacted with hydrogen to form HBr, which may be used to convert oxalateto oxalic acid.

Referring to FIGS. 29 and 30, an integratedacidification-esterification-hydrogenation system is shown. Carbondioxide, recycled acetonitrile (ACN) and tetrabutylammonium bromide(TBABr) or tetraalkylammonium halide (TBAX) may be fed into a catholyteregion of an electrochemical cell 2, such as described above, wherecarbon dioxide 1 is electrochemically reduced to formtetra-butyl-ammonium oxalate ((TBA)₂ oxalate, TBAO) or another oxalatesalt. An ACN solution, or other aprotic solvent solution, of TBABr(TBAX) and TBAO from the cathode compartment of the electrochemical cell(i.e., stream CATHOLYT 13) is withdrawn and fed into a reactiveextraction column 7. A halide or trihalide anion anolyte stream (notshown) may be withdrawn from the anode compartment of theelectrochemical cell 2, or electrochemical cell 2 may comprise ahydrogen oxidizing anode as described above.

The reactive extraction column 7 comprises two sections (“Acidify” and“Rxt-Ext” as indicated in FIG. 29). The column performs three functions:acidification, esterification, and extraction. See FIG. 30 for anillustration of the column 7. As shown in FIG. 30, the upper part of thecolumn is packed with structured packing 32, and it performsacidification of TBAO into oxalic acid (OA) using hydrogen halide vapor,HX, which flows in from the lower part of the Acidify section 35 of thecolumn while the catholyte stream is fed from the top of the columnthrough a liquid distributor to assure uniform distribution of theliquid. Pump-around can be applied from the bottom of this acidifyingsection to the top of the column to recycle fluids internally, asneeded, to ensure complete reaction of TBAO. This section of the columnhas in-situ energy integration where the heat released by theacidification reaction is used to vaporize the ACN without using anyheat transfer fluid or heat exchanger. ACN and unreacted HX 16 vents atthe top of the column. After a two phase FLASH, HX 30 is returned to theAcidify 35 section of the column, ACN 18 in the liquid stream is mergedwith another ACN 17 stream to recycle 29 back to the cathode compartmentof the cell 2.

The OA produced flows down with ACN to the lower section of the column 7for esterification with alcohol, such as 1-butabol (BOH). The alcohol 15is fed from the bottom of the column. As seen in FIG. 30, this sectionof the column does esterification and extraction simultaneously. The“Rxt-Ext” section of the column consists of alternative zones of packedsolid catalytic bed 33 (with Amberlyst 15, 35 or Zeolite Y) and unpackedrotating disks 34 for extraction. OA and BOH react to produce DBO andH₂O. As the products are formed, extraction action takes place, whichmeans that water continuously moves downwards with TBABr that has afavorable partitioning into aqueous phase while DBO, unreacted BOH andother trace organic species move up due to their lighter densities thanthat of water.

The side-drain feeding of OA+ACN+TBABr to RXT-EXT section 31 goes to thebottom of the reactive zone of the column for concurrent feeding of BOHwith OA, which enhances the extraction efficiency of the system as wellas the reaction efficiency due to the counter current flow of organicspecies and water. The downward flow of produced water concentrates BOHin organic phase that is moving up, which speeds up the esterificationreaction. The side-drain feeding of OA+ACN+TBABr to RXT-EXT 31 sectioncan also be split into more than one feeding points to optimize thecolumn performance.

As shown in FIG. 29, the bottom stream of the column is TBABr+H2O 20,which is fed into the top of a spray-drying crystallization tower 11through a liquid distributor with fine orifices. Hot air 23 is enteringfrom the bottom of the tower to evaporate water. The pelleted crystalform of TBABr or TBAX 21 is then recycled back to the cathodecompartment of electrochemical cell 2.

The intermediate product DBO 19 plus unreacted BOH 19 exits the upperend of the RXT-EXT section of the ACID-EST column, and enters DISTILLcolumn 10. In this DISTILL column 10, BOH is vaporized and recycled back28 to the Esterification section (Rxt-Ext section) of the ACID-ESTcolumn 7, while the DBO product 25 leaves at the bottom of the DISTILLcolumn 10 and then feeds into a fixed bed reactive distillation columnHYDROGN 12 for hydrogenation. This may be a reactive column that ispacked with solid Cu—Cr-oxide catalyst, compressed hydrogen 24 at 20 to50 atm entering from the bottom while DBO is fed from the top. Thecolumn has an optimum temperature profile. Product MEG 26 at fiber gradepurity of 99.9% exits from the bottom and regenerated BOH 22 is recycledback to the feeding stage of RXT-EXT section of the ACID-EST column 7.

It is understood that the specific order or hierarchy of steps in themethods disclosed are examples of exemplary approaches. Based upondesign preferences, it is understood that the specific order orhierarchy of steps in the method can be rearranged while remainingwithin the disclosed subject matter. The accompanying method claimspresent elements of the various steps in a sample order, and are notnecessarily meant to be limited to the specific order or hierarchypresented.

It is believed that the present disclosure and many of its attendantadvantages will be understood by the foregoing description, and it willbe apparent that various changes may be made in the form, constructionand arrangement of the components without departing from the disclosedsubject matter or without sacrificing all of its material advantages.The form described is merely explanatory, and it is the intention of thefollowing claims to encompass and include such changes.

What is claimed is:
 1. A method for reduction of oxalic acid intoproducts by a reactor, comprising: receiving a solution of oxalic acidin a reactor; receiving a feed of hydrogen in the reactor; reacting thesolution of oxalic acid and the hydrogen with a catalyst in the reactorat a temperature in a range of 50° to 170° C. to produce at least one ofglycolic acid or mono-ethylene glycol, the catalyst including at leastone of cobalt, copper, ruthenium, ruthenium dioxide, cobalt nickelalloys, nickel, Pt group metals, rhenium, copper chromite, zinc copperchromite, barium chromite, ammonium copper chromate, zinc chromate,Raney nickel, manganese chromate, and alloys thereof.
 2. The methodaccording to claim 1, wherein the reacting the solution of oxalic acidand the hydrogen with a catalyst includes stirring a mixture of a rateof 200 RPM to 800 RPM.
 3. The method according to claim 1, wherein thefeed of hydrogen is maintained at a pressure 300 psi to 1500 psi.
 4. Themethod according to claim 1, wherein the reactor is Teflon lined orglass lined.
 5. The method according to claim 1, wherein the reactorincludes Hastelloy, Hastelloy 276, Hastelloy C or Elgiloy
 6. A methodfor reduction of oxalic acid into products in an electrochemical cell,the electrochemical cell including a first region having a cathode and asecond region having an anode, the method comprising the steps of:contacting the first region with a catholyte comprising oxalic acid;contacting the second region with an anolyte; and applying an electricalpotential between the anode and the cathode sufficient to produce aglyoxylic acid recoverable from the first region.
 7. The methodaccording to claim 6, wherein the anolyte includes water.
 8. The methodaccording to claim 7, wherein oxygen is recoverable from the secondregion.
 9. The method according to claim 6, wherein the anolyte includesHX, where X is selected from a group consisting of F, Cl, Br, I andmixtures thereof.
 10. The method according to claim 9, wherein a halogenis recoverable from the second region.
 11. A method of reduction ofoxalic acid into products, comprising: receiving oxalic acid in areactive distillation column; receiving an alcohol in the reactivedistillation column; and reacting the oxalic acid with the alcohol inthe reactive distillation column, wherein a dialkyl oxalate is generatedfrom reacting the oxalic acid with the alcohol and is separated from asolution of the reactive distillation column in a section of thereactive distillation column.
 12. The method according to claim 11,wherein said alcohol is one of ethanol, butanol or methanol.
 13. Themethod according to claim 11, wherein the reactive distillation columnincludes an upper section, a middle section and a lower section.
 14. Themethod according to claim 13, wherein the dialkyl oxalate is generatedfrom reacting the oxalic acid with the alcohol and is separated from asolution of the reactive distillation column in the lower section of thereactive distillation column.
 15. The method according to claim 14,wherein the middle section includes an acid catalyst.
 16. The methodaccording to claim 15, wherein the oxalic acid is received in the uppersection of the reactive distillation column and the alcohol is receivedin the lower section of the reactive distillation column.
 17. The methodaccording to claim 11, further comprising: receiving the dialkyl oxalateat a hydrogenation device to produce a dialkyl oxalate reductionproduct.
 18. A method for producing a first product from a first regionof an electrochemical cell having a cathode and a second product from asecond region of the electrochemical cell having an anode, theelectrochemical cell having a separator that separates the first regionand the second region, the method comprising the steps of: contactingthe first region with a catholyte comprising carbon dioxide and anon-aqueous solvent; contacting the second region with an anolyte, theanolyte comprising MX and the non-aqueous solvent; and applying anelectrical potential between the anode and the cathode sufficient toproduce an oxalate recoverable from the first region and a halogenrecoverable from the second region.
 19. The method according to claim18, wherein the cathode is formed of one or more of metal plates, packedbed of metal spheres or fibers, screens, meshes, metal foams, metalnon-woven materials, sintered non-wovens, metal wools, sintered metalfibers, woven metal felts, metal woven fibrous materials, metal coatedcarbon materials and metal coated ceramic materials.
 20. The methodaccording to claim 18, wherein the anode is formed of one or more ofplates, RVC, carbon cloth, PTFE, carbon tissue, carbon felts, carbonfibers, conductive diamond films, iridium oxide on titanium, rutheniumoxide, graphine and graphite.
 21. The method according to claim 18,wherein the separator is formed of one or more of polymeric porousmaterials, inorganic filtration materials, perfluorinated ionomers,combination hybrid organic-Inorganic membranes, hydrocarbon basedmembranes and solid state ion conductors.
 22. The method according toclaim 18, where X is selected from a group consisting of F, Cl, Br, Iand mixtures thereof.
 23. The method according to claim 18, wherein thehalogen includes at least one of F₂, Cl₂, Br₂, I₂, F₃—, Cl₃—Br₃— or I₃—.24. The method according to claim 18, wherein the cathode includes atleast one of Al, Au, Ag, Bi, C, Cd, Co, Cr, Cu, Cu₂O, Cu, Fe, Ga, Hg,In, Mo, Nb, Ni, NiCo₂O₄, Ni—Fe, Pb, Pd Pt, Rh, Sn, Ti, V, W, Zn,stainless steel, austenitic steel, ferritic steel, duplex steel,martensitic steel, Nichrome, elgiloy Hastelloy, metal carbides andalloys thereof.
 25. The method according to claim 24, said cathodeincludes nickel or a nickel alloy.
 26. The method according to claim 18,wherein the non-aqueous solvent includes at least one of propylenecarbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate,dimethylsulfoxide, dimethylformamide, acetonitrile, ammonia, acetone,tetrahydrofuran, N,N-dimethylacetaminde, dimethoxyethane, diethyleneglycol dimethyl ester, butyrolnitrile, 1,2-difluorobenzene,γ-butyrolactone, N-methyl-2-pyrrolidone, sulfolane, 1,4-dioxane,nitrobenzene, nitromethane, acetic anhydride, alkanes, cycloalkanes,perfluorocarbons, linear carbonates, aromatics such as benzene andtoluene and their derivatives, dichloromethane, chloroform, ethers,chlorobenzene, polyols, glymes, diglymes, triglymes, tetraglymes,alcohols, alkenes, trifluorotoluene, anisole, m-cresol, and ionicliquids to include those containing cations of the types: 1,3dialkyimidazolium, N,N dialkylpyrrolidinium, and1-alkyl-2,3-dimethylimidazolium where N=2 or 4 and anions of the typehexafluorophosphate, tetrafluroborate,bis(trifluoromethanesulfonyl)imide, perfluoroalkylphosphate, and halideions such as Br—
 27. The method according to claim 18, wherein theoxalate is M_(N)C₂O₄, N is 1 or
 2. 28. The method according to claim 18,wherein M is Li⁺, Na⁺, K⁺, Ca⁺⁺, Ba⁺⁺, Sr⁺⁺, Mg⁺⁺, a R₁R₂R₃R₄N⁺, K⁻where each of R₁₋₄ is independently selected from the group consistingof alkyl, branched alkyl, cycloalkyl, and aryl, tetraalkyl ammonium,tetramethylammonium, tetraethylammonium, tetrabutylammonium,tetraphenylphosphonium, tetrabutylphosphonium, tetraethylphosphonium,tetrahexylammonium, tetraoctylammonium, methyl tributylammonium,butyltrimethylammonium, 1-n-butyl-3-methylimidazolium,1-ethyl-3-methylimidazolium, 1-ethyl-1-methylpyrrolidinium,di-n-decyldimethylammonium, choline, or ammonium.